摘要:

Journal of Analytical Atomic Spectrometry (Including Atomic Spectrometry Updates) JAAS Editorial Board* Chairman B. L. Sharp (Loughborough UK) J. M. Gordon (Cambridge UK) S. J. Haswell (Hull UK) S. J. Hill (Plymouth UK) R. C. Hutton (Winsford UK) D. Littlejohn (Glasgow UK) J. Marshall (Middlesbrough UK) D. L. Miles (Keyworth UK) A. Sanz-Medel (Oviedo Spain) *The JAAS Editorial Board reports to the Analytical Editorial Board Chairman J. N. Miller (Loughborough UK) JAAS Advisory Board F. C. Adams (Antwerp Belgium) R. M. Barnes (Amherst MA USA) L. Bezur (Budapest Hungary) M. W. Blades (Vancouver Canada) R. F. Browner (Atlanta GA USA) S. Caroli (Rome Italy) A. J. Curtius (Floriandpolis Brazil) J. B. Dawson (Leeds UK) M. T. C. de Loos-Vollebregt (Delft The Netherlands) L. Ebdon (Plymouth UK) M.S. Epstein (Gaithersburg MD USA) Fang Zhao-lun (Shenyang China) W. Frech (UmeA Sweden) A. L. Gray (Egham UK) S. Greenfield (Loughborough UK) G. M. Hieftje (Bloomington IN USA) B. V. L'vov (St. Petersburg Russia) R. K. Marcus (Clemson SC USA) J. M. Mermet (Villeurbanne France) T. Nakahara (Osaka Japan) Ni Zhe-ming (Beijing China) N. Omenetto (lspra Italy) C. J. Park (Taejon Korea) R. E. Sturgeon (Ottawa Canada) V. Sychra (Prague Czech Republic) R. Van Grieken (Antwerp Belgium) A. Walsh .K. B. (Victona Australia) B. Welz (Uberlingen Germany) Atomic Spectrometry Updates Editorial Board Chairman *D. L. Miles (Keyworth UK) J. Armstrong (Edinburgh UK) J. R. Bacon (Aberdeen UK) C. Barnard (Glasgow UK) R. M. Barnes (Amherst MA USA) S. Branch (High Wycombe UK) R.Bye (Oslo Norway) J. Carroll (Middlesbrough UK) M. R. Cave (Keyworth UK) S. Chenery (Keyworth UK) *J. M. Cook (Keyworth UK) *M. S. Cresser (Aberdeen UK) H. M. Crews (Norwich UK) J. S. Crighton (Sunbury-on-Thames UK) *J. B. Dawson (Leeds UK) J. R. Dean (Newcastle upon Tyne UK) *A. T. Ellis (Oxford UK) *E. H. Evans (Plymouth UK) J. Fazakas (Budapest Hungary) A. Fisher (Plymouth UK) *J. M. Gordon (Cambridge UK) D. J. Halls (Glasgow UK) *S. J. Hill (Plymouth UK) K. W. Jackson (Albany NY USA) R. Jowitt (Middlesbrough UK) K. Kitagawa (Nagoya Japan) J. Kubova (Bratislava Slovak Republic) *J. Marshall (Middlesbrough U K ) H. Matusiewicz (Poznan Poland) A. W. McMahon (Manchester UK) J. M. Mermet (Villeurbanne France) R. G. Michel (Storrs CT USA) T. Nakahara (Osaka Japan) Ni Zhe-ming (Beijing China) P.R. Poole (Hamilton New Zealand) P. J. Potts (Milton Keynes UK) W. J. Price (Budleigh Salterton UK) C. J. Rademeyer (Pretoria South Africa) *M. H. Ramsey (London UK) P. G. Riby (Greenwich UK) A. Sanz-Medel (Oviedo Spain) 'B. L. Sharp (Loughborough UK) I. L. Shuttler (Uberlingen Germany) S. T. Sparkes (Plymouth UK) R. Stephens (Halifax Canada) J. Stupar (Ljubljana Slovenia) R. E. Sturgeon (Ottawa Canada) *A. Taylor (Guildford UK) G. C. Turk (Gaithersburg MD USA) J. F. Tyson (Amherst MA USA) P. Watkins (London UK) B. Welz (Uberlingen Germany) J. Williams (Egham UK) J. B. Willis (Victoria Australia) *Members of the ASU Executive Committee Editor JAAS Janice M. Gordon The Royal Society of Chemistry Thomas Graham House Science Park Milton Road Cambridge CB4 4WF UK.Telephone + 44 (0) 1223 420066. Fax + 44 (0) 1223 420247. E-mail RSC1 @RSC.ORG (Internet) Senior Assistant Editor Brenda Holliday Editorial Secretary Lesley Turney US Associate Editor JAAS Dr. J. M. Harnly US Department of Agriculture Beltsville Human Nutrition Research Center Beltsville MD 20705 USA. Telephone 301 -504-8569 Assistant Editor Ziva Whitelock Advertisements Advertisement Department The Royal Society of Chemistry Burlington House Piccadilly London W1 V OBN UK. Telephone + 44 (0) 171 -287 3091. Fax + 44 (0) 171 -494 11 34. Information for Authors Full details of how to submit materials for publi- cation in JAAS are given in the Instructions to Authors in Issue 1. Separate copies are available on request. The Journal of Analytical Atomic Spectrometry (JAAS) is an international journal for the publi- cation of original research papers communi- cations and letters concerned with the development and analytical application of atomic spectrometric techniques.The journal is pub- lished twelve times a year including comprehen- sive reviews of specific topics of interest to practising atomic spectroscopists and incorpor- ates the literature reviews which were previously published in Annual Reports on Analytical Atomic Spectroscopy (ARAAS). Manuscripts intended for publication must describe original work related to atomic spectro- metric analysis. Papers on all aspects of the sub- ject will be accepted including fundamental studies novel instrument developments and prac- tical analytical applications.As well as AAS AES and AFS papers will be welcomed on atomic mass spectrometry X-ray fluorescence/emission spectrometry and secondary emission spec- trometry. Papers describing the measurement of molecular species where these relate to the characterization of sources normally used for the production of atoms or are concerned for example with indirect methods of analysis will also be acceptable for publication. Papers describing the development and applications of hybrid techniques (e.g.- GC-coupled AAS and HPLC-ICP) will be particularly welcome. Manuscripts on other subjects of direct interest to atomic spectroscopists including sample prep- aration and dissolution and analyte pre-concen- tration procedures as well as the statistical interpretation and use of atomic spectrometric data will also be acceptable for publication.There is no page charge. The following types of papers will be considered. Full papers describing original work. Communications which must be on an urgent matter and be of obvious scientific importance. Communications receive priority and are usually published within 2-3 months of receipt. They are intended for brief descriptions of work that has progressed to a stage at which it is likely to be valuable to workers faced with similar problems. Reviews which must be a critical evaluation of the existing state of knowledge on a particular facet of analytical spectrometry. Every paper (except Communications) will be submitted to at least two referees by whose advice the Editorial Board of JAAS will be guided as to its acceptance or rejection.Papers that are accepted must not be published elsewhere except by permission. Submission of a manuscript will be regarded as an undertaking that the same material is not being considered for publication by another journal. Manuscripts (three copies typed in double spacing) should be sent to Janice M. Gordon Editor JAAS or Dr. J. M. Harnly US Associate Editor JAAS. All queries relating to the presentation and sub- mission of papers and any correspondence regarding accepted papers and proofs should be directed to the Editor or US Editor (addresses as above). Members of the JAAS Editorial Board (who may be contacted directly or via the Editorial Office) would welcome comments suggestions and advice on general policy matters concerning JAAS.Fifty reprints are supplied free of charge. Journal of Analytical Atomic Spectrometry (JAAS) (ISSN 0267-9477) is published monthly by The Royal Society of Chemistry Thomas Graham House Science Park Milton Road Cambridge CB4 4WF UK. All orders accompanied with payment should be sent directly to The Royal Society of Chemistry Turpin Distribution Services Ltd. Blackhorse Road Letchworth Herts. SG6 lHN UK Tel. +44 (0) 462 672555; Telex 825372 Turpin G; Fax +44 (0) 462 480947. Turpin Distribution Services Ltd. is wholly owned by The Royal Society of Chemistry. 1995 Annual subscription rate EEA €312.00 USA $941.50 Canada f538.00 (+ GST) Rest of World f538.00. Customers should make payments by cheque in sterling payable on a UK clearing bank or in US dollars payable on a US clearing bank. Air freight and mailing in the USA by Publications Expediting Inc.200 Meacham Avenue Elmont NY 11 003. USA Postmaster send address changes to Journal of Analytical Atomic Spectrometry (JAAS) Publications Expediting Inc. 200 Meacham Avenue Elmont NY 11003. Postage paid at Jamaica NY 11431. All other despatches outside the UK by Bulk Airmail within Europe Accelerated Surface Post outside Europe. PRINTED IN THE UK. @The Royal Society of Chemistry 1995. All rights reserved. No part of this publication may be reproduced stored in a retrieval system or transmitted in any form or by any means electronic mechanical photographic recording or otherwise without the prior permission of the publishers.Journal of Analytical Atomic Spectrometry (Including Atomic Spectrometry Updates) JAAS Editorial Board* Chairman B.L. Sharp (Loughborough UK) J. M. Gordon (Cambridge UK) S. J. Haswell (Hull UK) S. J. Hill (Plymouth UK) R. C. Hutton (Winsford UK) D. Littlejohn (Glasgow UK) J. Marshall (Middlesbrough UK) D. L. Miles (Keyworth UK) A. Sanz-Medel (Oviedo Spain) JAAS Advisory Board F. C. Adams (Antwerp Belgium) R. M. Barnes (Amherst MA USA) L. Bezur (Budapest Hungary) M. W. Blades (Vancouver Canada) R. F. Browner (Atlanta GA USA) S. Caroli (Rome Italy) A. J. Curtius (Norianopolis Brazil) J. B. Dawson (Leeds UK) M. T. C. de Loos-Vollebregt (Delft The Nether L. Ebdon (Plymouth UK) M. S. Epstein (Gaithersburg MD USA) Fang Zhao-lun (Shenyang China) W. Frech (Urnei Sweden) A. L.Gray (Egham UK) S. Greenfield (Loughborough UK) G. M. Hieftje (Bloomington IN USA) B. V. L'vov (St. Petersburg Russia) R. K. Marcus (Clemson SC USA) J. M. Mermet (Villeurbanne France) T. Nakahara (Osaka Japan) Ni Zhe-ming (Beijing China) N. Omenetto (lspra Italy) C. J. Park (Taejon Korea) R. E. Sturgeon (Ottawa Canada) V. Sychra (Prague Czech Republic) R. Van Grieken (Antwerp Belgium) A. Walsh ,K. 6. (Victoria Australia) B. Welz (Uberlingen Germany) ids) Atomic Spectrometry Updates Editorial Board Chairman *D. L. Miles (Keyworth UK) J. Armstrong (Edinburgh UK) J. R. Bacon (Aberdeen UK) C. Barnard (Glasgow UK) R. M. Barnes (Amherst MA USA) S. Branch (High Wycombe U K ) R. Bye (Oslo Norway) J. Carroll (Middlesbrough UK) M. R. Cave (Keyworth UK) S. Chenery (Keyworth UK) *J.M. Cook (Keyworth UK) 'M. S. Cresser (Aberdeen UK) H. M. Crews (Norwich UK) J. S. Crighton (Sunbury-on-Thames UK *J. €3. Dawson (Leeds UK) J. R. Dean (Newcastle upon Tyne UK) *A. T. Ellis (Oxford UK) *E. H. Evans (Plymouth UK) J. Fazakas (Budapest Hungary) A. Fisher (Plymouth UK) 'J. M. Gordon (Cambridge UK) D. J. Halls (Glasgow UK) *S. J. Hill (Plymouth UK) K. W. Jackson (Albany NY USA) R. Jowi t t (Middlesbrough UK ) K. Kitagawa (Nagoya Japan) J. Kubova (Bratislava Slovak Republic) *J. Marshall (Middlesbrough UK) H. Matusiewicz (Poznan Poland) A. W. McMahon (Manchester UK) J. M. Mermet (Villeurbanne France) R. G. Michel (Storrs CT USA) T. Nakahara (Osaka Japan) Ni Zhe-ming (Beijing China) P. R. Poole (Hamilton New Zealand) P. J. Potts (Milton Keynes UK) W.J. Price (Budleigh Salterton UK) C. J. Rademeyer (Pretoria South Africa) *M. H. Ramsey (London UK) P. G. Riby (Greenwich UK) A. Sanz-Medel (Oviedo Spain) *B. L. Sharp (Loughborough UK) I. L. Shuttler (Uberlingen Germany) S. T. Sparkes (Plymouth UK) R. Stephens (Halifax Canada) J. Stupar (Ljubljana Slovenia) R. E. Sturgeon (Ottawa Canada) *A. Taylor (Guildford UK) G. C. Turk (Gaithersburg MD USA) J. F. Tyson (Amherst MA USA) P. Watkins (London UK) 6. Welz (Uberlingen Germany) J. Williams (Egham UK) J. 8. Willis (Victoria Australia) *Members of the ASU Executive Committee Editor JAAS Janice M. Gordon The Royal Society of Chemistry Thomas Graham House Science Park Milton Road Cambridge CB4 4WF UK. Telephone + 44 (0) 1223 420066. Fax + 44 (0) 1223 420247. E-mail RSCl @RSC.ORG (Internet) Senior Assistant Editor Brenda Holliday Editorial Secretary Lesley Turney US Associate Editor JAAS Dr.J. M. Harnly US Department of Agriculture Beltsville Human Nutrition Research Center Beltsville MD 20705 USA.. Telephone 301 -504-8569 Assistant Editor Ziva Whitelock Advertisements Advertisement Department The Royal SQciety of Chemistry Burlington House Piccadilly London W1 V OBN UK. Telephone + 44 (0) 171 -287 3091. Fax -1 44 (0) 171 -494 11 34. Information for Authors Full details of how to submit materials for publi- cation in JAAS are given in the Instructions to Authors in Issue 1. Separate copies are available on request. The Journal of Analytical Atomic Spectrometry (JAAS) is an international journal for the publi- cation of original research papers communi- cations and letters concerned with the development and analytical application of atomic spectrometric techniques.The journal is pub- lished twelve times a year including comprehen- sive reviews of specific topics of interest to practising atomic spectroscopists and incorpor- ates the literature reviews which were previously published in Annual Reports on Analytical Atomic Spectroscopy (ARMS). Manuscripts intended for publication must describe original work related to atomic spectro- metric analysis. Papers on all aspects of the sub- ject will be accepted including fundamental studies novel instrument developments and prac- tical analytical applications. As well as AAS AES and AFS papers will be welcomed on atomic mass spectrometry X-ray fluorescence/emission spectrometry and secondary emission spec- trometry.Papers describing the measurement of molecular species where these relate to the characterization of sources normally used for the production of atoms or are concerned for example with indirect methods of analysis will also be acceptable for publication. Papers describing the development and applications of hybrid techniques (e.g. GC-coupled AAS and HPLC-ICP) will be particularly welcome. Manuscripts on other subjects of direct interest to atomic spectroscopists including sample prep- aration and dissolution and analyte pre-concen- tration procedures as well as the statistical interpretation and use of atomic spectrometric data will also be acceptable for publication. There is no page charge.The following types of papers will be considered. f u l l papers describing original work. Communications which must be on an urgent matter and be of obvious scientific importance. Communications receive priority and are usually published within 2-3 months of receipt. They are intended for brief descriptions of work that has progressed to a stage at which it is likely to be valuable to workers faced with similar problems. Reviews which must be a critical evaluation of the existing state of knowledge on a particular facet of analytical spectrometry. Every paper (except Communications) will be submitted to at least two referees by whose advice the Editorial Board of JAAS will be guided as to its acceptance or rejection. Papers that are accepted must not be published elsewhere except by permission.Submission of a manuscript will be regarded as an undertaking that the same material is not being considered for publication by another journal. Manuscripts (three copies typed in double spacing) should be sent to Janice M. Gordon Editor JAAS or Dr. J. M. Harnly US Associate Editor JAAS. All queries relating to the presentation and sub- mission of papers and any correspondence regarding accepted papers and proofs should be directed to the Editor or US Editor (addresses as above). Members of the JAAS Editorial Board (who may be contacted directly or via the Editorial Office) would welcome comments suggestions and advice on general policy matters concerning JAAS. Fifty reprints are supplied free of charge. Journal of Analytical Atomic Spectrometry (JAAS) (ISSN 0267-9477) is published monthly by The Royal Society of Chemistry Thomas Graham House Science Park Milton Road Cambridge CB4 4WF UK.All orders accompanied with payment should be sent directly to The Royal Society of Chemistry Turpin Distribution Services Ltd. Blackhorse Road Letchworth Herts. SG6 IHN UK Tel. +44 (0) 1462 672555; Telex 825372 Turpin G; Fax +44 (0) 1462 480947. Turpin Distribution Services Ltd. is wholly owned by The Royal Society of Chemistry. 1995 Annual subscription rate EEA €51 2.00 USA $941 50 Canada f538.00 (+ GST) Rest of World f538.00. Customers should make payments by cheque in sterling payable on a UK clearing bank or in US dollars payable on a US clearing bank. Air freight and mailing in the USA by Publications Expediting Inc. 200 Meacham Avenue Elmont NY 11 003. USA Postmaster send address changes to Journal of Analytical Atomic Spectrometry (JAAS) Publications Expediting Inc. 200 Meacham Avenue Elmont NY 11 003. Postage paid at Jamaica NY 11 431. All other despatches outside the UK by Bulk Airmail within Europe Accelerated Surface Post outside Europe. PRINTED IN THE UK. @The Royal Society of Chemistry 1995. All rights reserved. No part of this publication may be reproduced stored in a retrieval system or transmitted in any form or by any means electronic mechanical photographic recording or otherwise without the prior permission of the publishers.

ISSN:0267-9477    

DOI:10.1039/JA99510FX005

出版商:RSC    

年代:1995

数据来源: RSC

摘要:

Journal of Analytical Atomic Spectrometry IIIII CONTENTS I NEWS PAGES Conference Report Daran Sadler Book Reviews David James Roberts Miguel de la Guardia Diary of Conferences and Courses Future Issues 15N 17N 18N 20N PAPERS Solid Sampling Electrothermal Vaporization Inductively Coupled Plasma Mass Spectrometry for the Determination of Arsenic in Standard Reference Materials of Plant Origin Frank Vanhaecke Sylvie Boonen Luc Moens Richard Dams Trace Enrichment and Determination of Gold By Flow Injection Inductively Coupled Plasma Spectrometry. Part II. Inductively coupled Plasma Mass Spectrometry M. M. Gomez Gomez C. W. Mcleod Direct Determination of the Samarium Neodymium Ratio in Geological Materials by Inductively Coupled Plasma Quadrupole Mass Spectrometry with Cryogenic Desolvation.Comparison with Isotope Dilution Thermal Ionization Mass Spectrometry Christian Pin Philippe Telouk Jean-Louis lmbert Optimization of Operating Conditions for Improved Precision of Zirconium and Hafnium Isotope Ratio Measurement by Inductively Coupled Plasma Mass Spectrometry Qianli Xie Rob Kerrich Determination of Organometallic Species by Gas Chromatography Inductively Coupled Plasma Mass Spectrometry Andreas Prange Eckard Jantzen Interference-free Determination of Selenium(iv) by Capillary Gas Chromatography-Microwave-induced Plasma Atomic Emission Spectrometry After Volatilization with Sodium Tetraethylborate M. Beatriz de la Calle Guntitias Ryszard lobinski Freddy C. Adams Matrix Effects in Argon Plasma on Elemental Analysis of Archaeological Glazes by Inductively Coupled Plasma Atomic Emission Spectrometry Lilli Paama Lindy Piiri Paavo Peramaki Lauri H.J. Lajunen Sequential Injection Analysis System for the Determination of Hydride-forming Elements by Direct Current Plasma Atomic Emission Spectrometry Paul Ek Stig-Goran Hulden Ari lvaska Spectrometer System for Simultaneous Multi-element Electrothermal Atomic Absorption Spectrometry Using Line Sources and Zeeman-effect Background Correction Bernard Radziuk Gunther Rodel Herbert Stenz Helmut Becker-Ross Stefan Florek Silver Matrix Effects on Gold Atomization in a Graphite Furnace Investigated by Two-dimensional Laser Imaging with a Gated Charge Coupled Device Camera Eric Masera Patrick Mauchien Yannick Lerat High-resolution Spectrometer for Atomic Spectrometry Stefan Florek Helmut Becker-Ross Capabilities and Limitations of Different Techniques in Electrothermal Atomic Absorption Spectrometry for Direct Monitoring of Arsenic Cadmium and Lead Contamination of Sea-water Enrique Alvarez-Cabal Cimadevilla Katarzyna Wrobel Alfredo Sanz-Medel Determination of Beryllium in Drinking and Waste Water by Tungsten Furnace Atomic Absorption Spectrometry TomaS Cernohorsky Stanislav Kotrly Investigation of Potentialities of Atomic Fluorescence Spectrometry With a Tantalum Coil Atomizer for Gas Monitoring Vladimir A.Khvostikov Svetlana S. Grazhulene Alfred Golloch Stefan Kirschner Ursula Telgheder 81 89 93 99 105 111 117 121 127 137 145 149 155 161 AT0 M I C S P ECTR 0 M ETRY U P DATES Environmental Analysis - Malcolm S.Cresser Janet Armstrong Jennifer M. Cook John R. Dean Peter Watkins Mark Cave References 9R 49R 0 2 6 7 - 9 1 7 7 ( 1 9 9 5 1 2 . 1 - 1 Typeset printed and bound by The Charlesworth Group Huddersfield England 01 484 51 7077Ramon M. Barnes Editor Department of Chemistry LGRC Towers University of Massachusetts Am herst MA 01 003-0035 Telephone (413) 545-2294 fax 545-4490 Objective The ICP lNFORMATION NEWSLETTER is a monthly journal published by the Plasma Research Group at the University of Massachusetts and is devoted exclusively to the rapid and impartial dissemination of news and literature information re- lated to the development and applications of plasma sources for spectrochemical analysis. Background ICP stands for inductively coupled plasma discharge which during the past decade has become the leading spectrochemi- cal excitation source for atomic emission spectroscopy.ICP discharges also are applied commercially as an ion source for mass spectrometry and as an atom and ion cell in atomic fluo- reswnw spectrometry. The popularity of this source and the need tocollect in a single literature reference all of the pertinent data on ICP stimulated the publication of the ICP INFOR- MATlON NEWSLETTER in 1975. Other popular plasma sources i.e. microwave induced plasmas direct current plasmas and glow discharges also are included in the scope of the ICP IN- FORMATION NEWSLETTER. Scope As the only authoritative monthly journal of its type the ICP INFORMATION NEWSLETTER is read in more than 40 coun- tries by scientists actively applying or planning to use the ICP or other types of plasma spectroscopy.For the novice in the field the ICP INFORMATION NEWSLETTER provides a cunase and systematic source of information and background material needed for the selection of instrumentation or the development of methodology. For the experienced scientist it offers a sin- gle-source reference to current developments and literature. Editorial The ICP lNFORMATlON NEWSLETTER is edited by Dr. Ramon M. Barnes Professor of Chemistry University of Mas- sachusetts at Amherst with the assistance of a 20-member Board of National Correspondents composed of leading plasma spectroscopists. The Board members from around the world report news viewpoints and developments. Dr. Barnes has been conducting plasma research on ICP and other dis- charges since 1968.He also serves as chairman of the Winter Conference on Plasma Spectrochemistry sponsored by the ICP INFORMATION NEWSLETTER. Regular Features *Original submitted and invited research articles by ICP and *Complete bibliography of all major ICP publications. *Abstracts of all ICP papers presented at major US and inter- .First-hand accounts of world-wide ICP developments. *Special reports on dcp microwave glow discharge and other Calendar and advanced programs of plasma meetings. *Technical translations and reprints of critical foreign-lan- guage ICP papers. *Critical reviews of plasma-related books and software. Conference Activities The ICP INFORMATION NEWSLETTER has sponsored seven international meetings on developments in atomic plasma spectrochemical analysis since 1980 in San Juan Orlando San Diego St.Petersburg and Kailua-Kona. Meeting pro- ceedings have appeared as Developments in Atomic Plasma Spectrochemical Analysis (Wiley) Plasma Spectrochemistry and Plasma Specfrochemistry 11-IV (Pergamon Press) as well as in special issues of Specfrochimica Acta Parts and Journal of Analytical Atomic Spectrometry. The 1994 Winter Confer- ence on Plasma Spectrochemistry will be held in San Diego California January 10 - 15 1994; its proceedings will be published by Fall 1994. Subscription Information Subscriptions are available for 12 issues on either an annual or volume basis. The first issue of each volume begins in June and the last issue is published in May. For example Volume 18 runsfrom June 1992 through May 1993.Backissues beginning with Volume 1 May 1975 also are available. To begin a subscription complete the form below and submit it with prepayment or purchase information. For additional informa- tion please call (41 3) 545-2294 fax (41 3) 545-4490 or contact the Editor. Credit cards accepted. plasma experts. national meetings. plasma progress. To order complete this section and send it to ICP Information Newsletter %Dr. Ramon M. Barnes Depart- ment of Chemistry Lederle GRC Towers University of Massachusetts Amherst MA 01 003-0035 USA. Start a subscription for the following issue 0 Volume(s)- (June 19- - May 19- ) or 0 19 (January - December). Enclosed D Prepayment 0 Check or money order QVISA 0 Mastercard Account No. (All 13 or 16 digits) ) or 0 Send invoice. Date Card holder Name Expiration date Card holder Signature .Amount Due $ Mail to NalW Organization Address City State/Country ZI P/Postalcode Telephone Telewfax Note For each credit-card transaction a 4 % service charge will be added reflecting our bank charges. Current subscription rates are $60 (North America) $85 (Europe South America) or $94 (Africa Asia Indian/Pacific Ocean Areas Middle East and Russia). Back issue rates available on request. All payments should be made with US dollars by draft on a US bank by international money order or by credit card. Foreign bank checks are not accepted. D Purchase order (No.

ISSN:0267-9477    

DOI:10.1039/JA99510BX007

出版商:RSC    

年代:1995

数据来源: RSC

摘要:

Atomic Spectrometry Update Atomic Spectrometry Update- Environmental Analysis MALCOLM S. CRESSER" Department of Plant and Soil Science Aberdeen University Meston Building Old Aberdeen UK AB9 2UE JANET ARMSTRONG Forth River Purijication Board Heriott Watt Research Park Avenue North Riccarton Edinburgh U K EH14 4AP JENNIFER M. COOK British Geological Suroey Keyworth Nottingham UK NG12 5GG JOHN R. DEAN Department of Chemical and Life Sciences University of Northumbria at Newcastle Ellison Building Newcastle upon Tyne UK NE1 8ST PETER WATKINS Department of Geology Imperial College of Science Technology and Medicine Royal School of Mines Prince Consort Road London UK SW7 2BP MARK CAVE British Geological Survey Keyworth Nottingham UK NGl2 5GG SUMMARY OF CONTENTS 1. 1.1. 1.2. 1.3.2. 2.1. 2.1.1. 2.1.2. 2.1.3. 2.14. 2.2. 2.2.1. 2.2.2. 2.2.3. 2.2.4. 2.2.5. 3. 3.1. 3.2. 3.2.1. 3.2.2. 3.2.3. 3.2.4. 3.2.5. 3.2.6. Air Analysis Sample Collection and Pretreatment Particle Characterization Instrument a1 Analysis Table 1. Summary of Analyses of Air and Particulates Water Analysis Sample Preparation Sample collection Separation and preconcentration procedures Hydride and cold vapour generation Speciation Instrumental Analysis Atomic absorption spectrometry Atomic emission X-Ray fluorescence Mass spectrometry Atomic fluorescence spectrometry and related techniques Table 2. Summary of Water Analyses Analysis of Soils Plants and Related Materials Soil and Plant Reference Materials Sample Preparation Sample dissolution Novel extraction procedures Solvent extraction Other preconcentration procedures Speciation studies Direct analysis of slurry samples This is the tenth annual review published in JAAS of the applications of atomic spectrometry to the chemical analysis of environmental samples. The format used is similar to that of previous years.Over the past 12 months there has been a further increase in the exploitation of the analytical power of ICP-MS and MS techniques generally. In the analysis of air this bas resulted in some interesting developments in the use of mathematical models to establish the origins of airborne particulates. Characterization of individual particulates also seems to be attracting more attention from researchers. In water analysis development of improved separation and preconcentration techniques and of speciation procedures still * Review Co-ordinator to whom correspondence should be addressed.3.3. 3.4. 3.5. Developments in Mass Spectrometry 3.6. Developments in X-Ray Spectrometry 3.7. Nuclear Techniques Developments in Atomic Absorption Spectrometry Developments in Atomic Emission Spectrometry Table 3. Summary of Analyses of Soils Plants and Related Materials 4. Analysis of Geological Materials 4,l. Introduction 4.2. Sample Preparation 4.2.1. Solid sample introduction 4.2.2. Decomposition with acids 4.2.3. Decomposition using fusion 4.2.4. Separation and preconcentration 4.2.4.1. Solvent extraction 4.2.4.2. Ion exchange 4.2.4.3. Coprecipitation 4.2.4.4. Vapour generation 4.2.4.5. Other separation methods 4.3. Instrumental Analysis 4.3.1.Atomic absorption spectrometry 4.3.2. Atomic fluorescence spectrometry 4.3.3. Atomic emission spectrometry 4.3.4. 4.3.5. Other mass spectrometric methods 4.3.6. X-Ray methods 4.3.7. Neutron activation analysis Inductively coupled plasma mass spectrometry Table 4. Summary of Analyses of Geological Materials consume a good deal of time. With the wider use of ICP-MS understanding of polyatomic ion interference effects is continuing to improve. For soils plants and geological materials the year has been one dominated largely by consolidation of existing methodology rather than one full of exciting new developments. 1. AIR ANALYSIS Over the past review year a substantial number of papers have been published which consider different aspects of sample collection and pretreatment for airborne gases and particulates.However in the area of instrumental development for this field little of novel interest has been described. Last year the paucity of papers in the area of particle characterization was Journal of Analytical Atomic Spectrometry February 1995 Vol. 10 9Rnoted (94/2403). That situation has been reversed this year with a substantial number of authors looking at individual particle characterization or using mathematical models to determine the sources of airborne particulates. This is reflected in Table 1. 1.1. Sample Collection and Pretreatmot The use of filters for sample collection is widespread and the development of suitable certified reference materials for method validation is vital. Attempts have been made to prepare high volume uniform filter deposits for analysis by XRF and batches are being prepared for characterization (94/649).Various workers have reported optimized sampling procedures prior to analysis by XRF. A comparison of thin layer and thin tablet methods showed that thin tablets prepared after grinding the dust to 5-7 pm gave more reproducible results when analysed by EDXRF (94/1561). Salva et al. (94/1601) analysed minute amounts of airborne particulate matter collected from small air volumes and within short sampling times by TXRF. The sample was collected either on membrane filters or by cascade impaction onto flat plexi-glass carriers. A portion was punched out of the membrane filter placed on a glass carrier and swollen with tetrahydrofuran. Evaporation of the solvent led to a thin film which was spiked with an interns€ standard whereas internal standard was added directly to the dust collected on the plexi-glass carrier no other treatment being necessary prior to analysis by TXRF.An alternative means of collecting samples for TXRF has been proposed by Dixkens et al. (94/659). They used an electrostatic precipitator which was able to concentrate sub- micron particles homogeneously on a spot of the XRF sample support. The collection of 100% of the particles with diameters less than 1 pm at a flow rate of 1.3 1 min-' is valuable for monitoring the heavy metal contents of sub-micron particles. Electrodeposition of Pt in dust digests was performed by Beinrohr et al. (94/1643) to improve the sensitivity of the determination of this element by ETAAS.Dust samples were initially digested with HN03 and HCl under pressure. The Pt in the digest solution was electrochemically deposited at -0.9-1.2 V onto a pyrolytically coated graphite tube packed with reticulated vitreous carbon. T h s filling had been axially bored to allow the light beam to pass through during AAS measurement and the opening plugged with a glass rod during the electrodeposition step. A number of solvent extraction procedures have been reported over this review year. Cryptand (2.2.1) in nitrobenzene was used to extract Cd from aqueous solutions at pH 6.5 with Rose Bengal as the counter ion. Cadmium was then stripped from the organic phase using 0.1 mol 1-' H2S04 and deter- mined by AAS. This method enabled separation of Cd from Co Cr Cu Fe Hg Mn Ni and Pb (94/83).Mercury in the workplace environment of a chlor-alkali plant was collected on activated carbon with a personal sampling pump (94/1854). The carbon was mineralized by heating with KMnO and H,S04. The Hg2+ ion was chelated with APDC and extracted with IBMK at pH 1.6-5. The extracted chelate was decom- posed with H2S04 prior to reduction to Hg with SnC1 and determination by CV-AAS. Trace amounts of Ni in welders' workplace environment were determined by FAAS following solvent extraction (94/2347). Solutions of Ni" in an alkaline medium and mol I-' BPKPH in ethanol gave a green chelate. Samples analysed by this method were diluted only 25-50 times which allows the analysis of air samples taken over a period of just a few minutes.Polyacrylate superabsorbent polymers were determined in air by precipitation with Cu (94/779). Sample was collected on PVC membrane filters and treated with 0.07 mol 1-l CU(CH~COO)~ solution to form a Cu-polymer precipitate. This was digested with HNO and HClO prior to determi- nation of Cu by ICP-AES. The detection limit for various polymers was 4.4-14 pg per sample. An on-line preconcentration system was used to determine trace levels of Cu in vehicle exhaust particulates (94/133). The Cu in aqueous solution was preconcentrated on an oxine- loaded activated carbon column and eluted with 4 mol 1-' HNO for determination by AAS. No interference was observed from Al Fe Ga and Mo but Nb Ni and V were possible interferents. An automated method for determining SO in air has been developed (94/324).The sample containing trapped determin- and was acidified with 6 mol 1-' HCl and the SO2 was reduced to H2S by NaBH,. A continuous flow system carried the sample and reagents into a gas-liquid separator where the H2S was swept by N2 into a cool H2-N,-entrained flame. The blue diatomic S2 emission generated was measured at 384 nm. Two papers on slurry hydride generation have been published in this review year. Nerin et al. (94/160) prepared a slurry of coal fly ash in water. An aliquot of the slurry was introduced to the hydride generator where the As was reduced by NaBH,. The method has been optimized with respect to acidity NaBH concentration Ar flow rate particle size and the influence of surfactants on slurry stability.The most critical factor was particle size which must be <8.5 pm. In the second paper (94/2346) both As and Hg were determined in coal fly ash slurries. The results obtained for both analytes agreed well with those obtained following dissolution. The authors con- cluded that the Hg appeared to be in an easily available form whilst quantitative recovery of As depended on small particle size and pretreatment of the slurry with iodide in an acidic medium. Mercury in air has been determined by amalgamation with gold coated onto tungsten wire loops (94/C2018). These were subsequently inserted into a modified ICP torch about 10 cm below the plasma and electrical power applied to the loop thus releasing the Hg. 1.2. Particle Characterization The number of papers published each year on topical issues varies substantially.In last year's review (94/2403) particle characterization received only passing comment whereas this review year several papers covering this area were published. Source and pathway characterization of lead in the environ- ment can be made using the isotope ratios of lead. Determination of the 206Pb ,07Pb isotope ratio by ICP-MS helped to assess the source of raised lead levels in children's blood (94/984). Two dust samples had lead isotope ratios similar to that found in the children's blood. Lead isotope ratios were also employed to determine the source of lead in aerosols collected over the North Sea following optimization studies to yield sufficient precision (94/2588). The Fine Particle Network in the eastern USA collected and determined by WDXRF the elemental concentrations in fine particles over two periods of several months (94/2417).This work allowed a database of fine particle composition to be developed and seasonal averages to be calculated. It is often necessary to apply mathematical models to analyt- ical results in order to identify potential sources of airborne particulates. Principle component analysis was applied to the data collected following INAA and AAS analysis of air samples collected whilst on board a ship on the Black Sea (94/358). Similarly principle component analysis as well as linear correlation coefficients and enrichment factors were applied to the interpretation of INAA and EDXRF data for 23 elements collected on filters in Sao Pado (94/2418).Chemometric evaluation of results of a three year study of the amount and composition of dust in an industrial residential conurbation in East Slovakia was performed by Florian et al. 10 R Journal of Analytical Atomic Spectrometry February 1995 Vol. 10Table 1 SUMMARY OF ANALYSES OF AIR AND PARTICULATES ~ Reference 941897 9411024 94/ 160 9412346 9412923 9412692 9412743 9418 3 94/59 9411 801 941133 941779 941196 9411854 94/C2018 9412346 9412572 94/59 941283 5 9412347 941984 9412552 941258 8 94 f 1643 9412794 941324 94/92 94/61 6 941845 94/24 941101 1 Technique; atomization; analyte form* AA;-;- NAA;-;- NAA;-;- AA;-;L AA;F Hy;Sl AA;- Hy;Sl A&- Hy;G MS;-;- MS;-z- AA;-;L Sample treatment/comments Quartz fibre filters used. Pretreatment procedure Sample collected on quartz fibre filters and digested with Aqueous slurry used for HG.Particle size of <8.5 pm essential Slurry treated with iodide in acidic solution to give satisfactory recoveries Development of proposed international standard for determining particulate As and As"' in workplace air Samples collected with ultra-efficient cryogenic trap. Isotope ratios for C and 0 measured Balloon-borne cryogenic sampling method. Accelerator MS used Cd extracted from solution with cryptand in C,H,NO,. Stripped from organic phase with H2S04 Cr concentration lower in grinding dust than welding fumes Health consequences of differing levels of exposure assessed Preconcentration on oxine-loaded activated C column and elution with 4 mol 1-' HNO (4.4 ng cm-,) Polymers collected on PVC membrane filter treated with Cu acetate solution; precipitate digested with HPH202 gave rapid generation of Hg for toxicokinetics Activated C used for sample collection; digested with required for INAA as Si interfered HCl-HNO3-HClO4 HNO,-HClO4 study KMn04-H2S04.HgZf chelated with APDC extracted with IBMK. Chelate digested with H2S04 prior to CVAAS (0.14 ng 1-') Wire loops coated with Au used to collect Hg; loop inserted into modified ICP torch. Electrical power applied to loop and Hg released thermally. Results compared with those from CVAAS Good recovery due to analyte being readily available. See As ref. 94f2346 Particulate I collected on particle filter; HI and I on NaOH-impregnated filters; H I 0 on tetrabutylammonium hydroxide-impregnated filters; organic I on activated charcoal filter welding fumes.See Cr ref. 94/59 purified; N20 trapped on zeolite bed prior to thermal desorption into GC carrier stream. Isotope ratio MS performed Filter treated with HNO,; extract adjusted to pH 7 prior to extraction with BPKPH-IBMK. Organic layer introduced to flame source of Pb in blood Mn concentration lower in grinding dust than in CO and H20 removed; N chromatographically HN0,-HClO digest. Isotopic ratios measured to assess Single pulse obtained for individual particles Isotope ratios used for source and pathway characterization. Optimization of ICP-MS needed to attain required precision chemical deposition of Pt onto graphite tube packed with reticulated vitreous carbon HN0,-HCl digestion under pressure prior to electro- Method and results presented Trapped SO reduced to H2S with NaBH4.Solution acidified with HC1; H,S swept by N into cool H,-N,- entrained air flame concentrations found by IC HPLC coupled to FAAS. System optimized to attain required detection limits Sample fused with KOH at 650°C residue dissolved in HC1. Further dilution with 10% KOH Victoria Blue B complex extracted into toluene from HC1 Standard additions method modified to extend linear. range for XRF; results compared with those from Total Se level compared with SeO,'- and Se04'- Glass fibre filters leached with HPLC mobile phase. ICP-AES Element A1 A1 As As As co C Cd Cr Cr cu c u Hg Hg Hg Hg I Mn N Matrix Aerosols and urban Aerosol Fly ash Coal fly ash Workplace air Atmosphere Stratospheric C 0 2 Aerosol Welding fumes dust Electroplating workplace air Vehicle exhaust particulates Polyacrylate superabsorbent particulates polymers Hg vapour Industrial workplace air AA;-;- AA;ETA- AA;-;L AE;ICP;L AA;CV;G AA;CV;G Air AE;ICP;G AA;CV;G Coal fly ash Atmospheric I species AA;CV;Sl IDMS;-- AA-;- MS;-;G Welding fumes dust Atmosphere Welding fumes AA;F;L Ni Pb Dust MS;ICP;L MS;ICP;S MS;ICP;- Pb Pb Airborne particles Air particulates Pt Dust A A;ETA;L Automotive catalyst exhaust Air MS;ICP;- Molecular emission;F;G -;ICPL AA;F air-C,H,;L Coal fly ash Organotin aerosol Se Sn AA;ETA;L Sn T1 Zn Dust Flue dust Fly ash Liquid scintillation;-;L AE;ICP;L XRF;-;- Journal of Analytical Atomic Spectrometry February 1995 Vol.10 1 1 RTable 1 (continued) Technique; atomization; analyte form* Sample treatment/comments Element Matrix Zn Airborne particles Various Urban dust Reference 94/25 52 94/55 MS;ICP;S See Pb ref.9412552 AA;F;- Sample collected in H20 or CH30H. Evaporated to AA;- Hy;- AE;spark;- AEdouble plasma;- dryness prior to analysis XRF;-;- AA;-;- Various (9) Tropospheric aerosols Cascade impactors used for sampling. Principal component analysis indicated analyte source No increase observed as a consequence of burning oil wells in Kuwait Characterization of geometrical properties 9417 1 941124 941178 941200 9412 18 941263 941358 941649 941658 Various (7) Air Various Agglomerated aerosol Various ( 5 ) Street and house dust particles AE;ICP;- AA;-;- 106 samples taken. Results suggest motor vehicles major Deposits in apparatus studied to indicate suitable means Samples collected by two-stage sampler.Enrichment in Principal component analysis of results. West Black Sea High volume uniform filter deposits checked prior to Size fractionated samples collected with cascade source (Cd Cr Ni Pb Zn) of cleaning fine particles had higher anthropogenic influx than east preparing batches for XRF INAA or PIXE analysis impactor. Filter papers digested in 65% HNO,; solution pipetted onto quartz sample carrier for TXRF Electrostatic precipitator collects sub-pm particles for direct analysis by TXRF Chemical speciation used to assess impact of air pollutants on health (Al Fe Zn) Samples studied on basis of different anthropogenic activities in five regions (Cd Cu Ni Pb) On-line elemental analysis of single particles Particles of less than 10 pm analysed Various Compressed air apparatus AA;-;- AA;-;- Various (4) Workplace dust Various Airborne particles Various (6) Aerosol filter RM Various (25) Airborne particulates Various Various (3) Various (4) Various Various Exhaust gases urban air Aerosols Air Single aerosol particles Atmospheric aerosols XRF;-;S 941659 941852 941853 941854 941895 941901 941 1 042 941 109 1 94/1186 9411345 94/1561 9411569 9411601 9411656 9411756 9411783 94JC2027 9412131 9412158 941241 5 94/24 1 6 94/24 17 A&-;- AAF air-C2H2; Various Various Atmospheric particulates Airborne particulates 3 step extraction procedure described for PIXE analysis of glass fibre filters Sample mixed with Li,C03 and graphite powder ( I + 1 +2) prior to analysis by conventional AES.For ALAS sample digested with HN0,-H20 (1 + 1) Diflerent radionuclide excitation sources compared Ambient air sucked into plasma to give on-line real time Depth-resolved chemical characterization analysis (Be Cd Co Pb) Gravitational dust Dust fly ash Environmental microparticles Gravitational dust Aerosol particles Airborne particulates Pollen dust Coal fly ash XRF;-;- AE;ICP;S Various (10) Various (4) Various Various Various Various Various Various (6) SNMS,SIMS; plasma;- XRF;-;- Optimization of sample preparation by thin-layer and Bulk composition by EDXRF; individual particles by Membrane filters and cascade impaction on flat Use of pollen for biomonitoring for heavy metal Digestion with HN03-HF at 140 "C for 20 h compared thin-tablet techniques described EPXMA and micro-PIXE plexiglass carriers compared for TRXRF pollution with dry ashing (As Cd Hg Sb Th Zn) XRF;-;S PIXE; -; - XRF;-;S XRF;-;- AA;-;- A&ET&L A&- Hy;G AA;CV;G AA;F;L NAA-;- XRF;-;- AE1CP;- AE;ICP;L AA;ETA;L AAF;- NAA;-;- AE;ICP;L Radioactive aerosols Results used to assess annual intakes Various Filters sonicated at 95 "C with 5 mol 1-' HCl+ 3 mol Factor analysis employed to determine main sources l-' HNO Various (12) Various Various (4) Various (10) Airborne particles hrborne particulates Fly ash Dust Microwave digestion of sample.ICP-AES optimized Geologically biased enrichment factors used to assess using simplex strategy source of dust NA.A-;- -;ICP;- XRF;-;- XRF;-;- NAA-;- XRF;-; Airborne particulates Fine particles Cluster analysis of data from dust from two locations Network of sites to monitor fine particles over several showed similarities in elemental composition sampling periods; WDXRF used for analysis Various Various 12 R Journal of Analytical Atomic Spectrometry February 1995 Vol.10Table 1 (continued) Element Various (23) Various Various (9) Various Various Various Various Various Various voc Matrix Aerosols Cod fired power plant emissions Air particulates Air particulates Coal mine dust Air and dust Airborne particulates fly ash Aerosols in gases Steel making flue dust Air Technique; atomization; analyte form* XRF;-;- NAA;-;- XRF;-;S XRF;-;S XRF;-;S MS;laser microprobe;S NAA;-;- MSiICPi- XRF;-;- MS;ICP;- AE;laser;L S AE;ICP;S Sample treatment/comments Dichotomous sampler used; data analysed for Hazardous element sampling train used with activated Enrichment factors for elements in air in Nairobi Li,BO beads doped with known amounts of characterization of source charcoal-impregnated filters examined appropriate elements for instrument variability compensation between sample runs Characterization of individual particles described Review of nuclear related analytical techniques used in environmental monitoring Several ICP-MS applications presented Gases passed through capillary; emerging particles Spark ablation of powder pellets prepared from sample atomized by laser pulse + graphite (1 + 1).Results compared with those from nebulized solutions Review of methods for VOC analysis ~~~~ Reference 941241 8 9412452 9412453 9412 59 7 9412644 94/28 16 9412852 94/2 8 69 94/29 13 9412 12 * Hy indicates hydride and S L G and S1 signify solid liquid gaseous or slurry sample introduction respectively.Other abbreviations are listed elsewhere. t Values in parentheses are detection limits. (94/1042). Dust deposits were analysed by conventional AES after mixing the sample with Li,CO and graphite powder whilst airborne dust was analysed by AAS following digestion with 5% HNO,. Different aerosol sources were identified for samples collected over the North Sea using multivariate statisti- cal analysis of EDXRF data which yielded bulk compositions of 15 elements (94/1569). Micro-PIXE and EPXMA were used to analyse individual aerosol particles. Single particle analysis was performed on coal mine dust using laser microprobe mass spectrometry (94/2644).This helped overcome the problems of correlating toxicity with conventional physicochemical data. The single particle approach was necessary to account for heterogeneity down to the level of individual particles. A method has been developed to identify iodine-containing species in the atmosphere (94/2572). Particulate I was collected on a particulate filter; HI and I were trapped by a NaOH impregnated filter; H I 0 species were adsorbed on tetrabutyl- ammonium hydroxide impregnated filter; and organoiodine compounds were trapped on activated charcoal. The I species were determined using ID-MS and the distribution pattern for each species assessed for different sampling locations.1.3. Instrumental Analysis A liquid chromatograph - FAAS system has been optimized for FAAS parameters such as air:C,H ratio and burner height using multivariate methods to enable organotins to be monitored at the required threshold occupational exposure level (94/616). The samples were collected on glass fibre filters which were sonicated in the HPLC mobile phase. The solutions were filtered prior to injection into the HPLC- FAAS system. A variety of excitation sources for EDXRF have been examined for analysing gravitational urban dusts (94/1091). The sources tested were based on 238Pu lo9Cd and 241Am. The Io9 Cd source gave the optimum response enabling Rb Sr and Zr to be detected though at the expense of less favourable detection limits for six other elements compared with when 238Pu was used.Measurements were made with a Si(Li) detector and multi-channel analyser. The determination offemtogram amounts of Pb and Zn in individual airborne particles has been achieved (94/2552). A single pulse was obtained for each particle by replacing a high- speed pre-amplifier in an ICP-MS with a pre-amplifier with a longer time constant followed by a bandpass filter. Between run instrumental variations for XRF analysis give rise to problems in quantification. Vitrified Li,B04 beads doped with known amounts of appropriate elements could be used to compensate for such variations (94/2597). Such beads could also be used as the equivalent of standard filters in the re-calibration of instruments. Nore et al. (94/1186) have proposed an ICP-AES type instrument which enables on-line real time analysis of air quality with respect to metallic aerosol concentrations. Ambient air was sucked into the plasma torch by a high throughput pump placed downstream of the plasma area.Secondary air was introduced downstream of the plasma to cool the gas and dilute the nitrogen oxides formed in the discharge. Calibration was by standard nebulized solutions and the determinands were Be Cd Co and Pb. 2. WATER ANALYSIS From assessing current trends in the analysis of natural waters it appears that frontier research is addressing two problems in particular the determination of trace elements in sea-water and the speciation of individual elements. Consequently the emphasis has been directed towards more sensitive elemental detection coupled to appropriate separation/preconcentration techniques.The ICP-MS and TXRF techniques are making significant contributions towards detection while chromato- graphic and vapour generation techniques provide the basis of many separation methods. 2.1. Sample Preparation 2.1.1. Sample collection It is not common for analytical methods to stress the impor- tance of good sample collection methodology. Therefore in the current review year it is encouraging to note that several papers emphasize the use of specific materials and the exacting cleaning handling and preservation procedures necessary for Journal of Analytical Atomic Spectrometry February 1995 Vol. 10 13Rthe collection of samples of wet precipitation (94/715 94/841 94/1736 94/1762).Attempts were also made to apportion the total amount of trace metals deposited between dissolved and particulate phases. In a Japanese study 100 ml aliquots of rain water were collected in a fraction collector filtered through a 0.45 pm membrane filter and concentrated by a factor of ten by rotary evaporation (94/715). Both filtrate and the particu- late matter were decomposed by HCl-HF prior to analysis by ICP-AES for 12 elements. As observed in the last review period microwave pretreatment can also be used where total elemental fluxes are required (94/1723). A protocol for minimizing contamination during collection filtration and analysis of trace metals in freshwater from Lake Ontario (USA) was described (94/1816). Samples were obtained using a portable clean laboratory and analysed in a Class 100 pressurized room.With these improved procedures much more distinctive trace element profiles could be discerned and the results have cast doubt on much of the published trace metal data for the Great Lakes. 2.1.2. Separation and preconcentration procedures Separation and preconcentration procedures are often required to improve LODs for the determination of trace elements in natural waters especially sea-water almost irrespective of the analytical tool employed. However many of the methods described in this category are directed towards FAAS because of the relative insensitivity of this technique. As a consequence there is little new in many of the papers published in this review year and the reader is directed to Table 2 for descriptions of the methods employing various chelating and ion-exchange resins.Of note was a Chinese paper describing the synthesis of a mercaptoacetamide resin from PVC and its capability to selectively absorb Au and Pt from water samples (94/209). The determinations of Cd Cu Pb and Zn by FAAS after three different preconcentration methods straight evaporation chel- ation with ammonium pyrrolidine dithiocarbamate and Dowex 50 cationic exchange resin were compared with direct measure- ment by ETAAS (94/2546). On-line preconcentration pro- cedures have been developed using columns of quinolin-8-01 for the determination of Al Ga and In by FAAS (94/553). Complexation of these elements with different buffering reagents was studied and conditions were optimized to give an enrichment factor of between 70 and 80 and LODs of approximately 3 ng m1-l.Other separation techniques listed in Table 2 include co-precipitation flotation and sorption by solids. Procedures employing co-precipitation have been directed towards the determination of heavy metals and have involved the use of manganese dioxide (94/1044) cerous hydroxide (94/1089) and alkaline magnesium nitrate (94/2298). As noted in last year's review cotton fibres are popular in China as a solid sorbant for Cd Cu Pb and Zn (94/1260 94/1624). Increasing use is being made offlow injection techniques in combination with on-line sample preconcentration and matrix modification particularly for the analysis of saline matrices. Therefore a review by Atienza et al.with 78 references of the analysis of sea-water by FI is very timely (94/383). The authors report that chelating resins of different types are the most common media used for sample preconcentration in FI systems. One of the more novel approaches by a group of Canadian workers was the use of a liquid membrane emulsion to precon- centrate Cd Co Cu Fe Mn Ni Pb and Zn from various liquids including waters for FAAS determination (94/730). The liquid membrane emulsion consisted of a water-in-oil emulsion of Span 80 2-ethylhexyl phosphoric acid mono-2- ethyl hexylester and di-2-ethylhexyl phosphoric acid kerosene and an aqueous solution of 1 mol 1-l HCl and 0.02 mol 1-' H,SO,. Although the authors claimed that the results were within klO% of data obtained by ETAAS the advantage of this method over more conventional schemes for the analysis of waters is not obvious.2.1.3. Hydride and cold vapour generation The fact that a considerable number of papers on the determi- nation of mercury by vapour generation still find their way into the literature is more of a guide to the environmental interest in this element and the difficulty in setting up a reliable preconcentration step rather than an indication of new developments in this area. An evaluation of CVAAS non- dispersive AFS and helium MIP-AES for the determination of Hg after collection on a gold amalgam trap demonstrated that results by all three techniques for the river water CRM ORMS-1 agreed with the certified value (94/765). A different approach involved the use of organized media (micelles and vesicles) to improve the kinetics of the Hg vapour generation (94/22OO).Didodecyldimethylammonium bromide (DDAB) was found to give the best detection limits. When DDAB vesicles were used in conjunction with a commercially available on-line membrane drying tube in the CV generation system detection limits of 0.2 ppb were obtained by both ICP- AES and AAS representing an improvement of about a factor of 3. Gold is often employed to preconcentrate Hg prior to the final detection step. A Chinese group coated their graphite tubes with palladium chloride which provided the surface for in-situ preconcentration of the Hg vapour at 250°C; Hg was then atomized at 2200 "C (94/241). One interesting if expensive extension of this idea is to trap the Hg on a gold-coated graphite tube which was connected to a continuous flow HG apparatus prior to measurement by ETAAS (94/720).The Chinese authors claim this method is simple and convenient with a detection limit of 0.8 ng 1-l. Hydride generation can be applied with advantage to a number of volatile elements. A review in Japanese with 20 references details both batch and continuous type apparatus for the determination of As Bi Ge Pb Sb Sn and Te by AAS (94/143). A Slovakian review of HG-AES techniques for As containing 43 references recommended continuous HG with the use of a cryogenic trap for the detection of extremely low concentrations of As (94/1040). In-situ preconcentration in a modified graphite tube as described above for trapping Hg vapour can be applied with equal success to the determination of hydrides by ETAAS.Considerable interest in this technique has been evident this review year. Burguera and Burguera (94/283) developed an FI-ETAAS method for total As and its species by trapping the arsine in a Pd-coated graphite tube at 200°C; an LOD of 1Opg of As was recorded for a variety of water types. Veber et al. (94/2925) achieved an LOD of 0.02 pg 1-l for both As and Se in mineral waters by preconcentration of the hydrides in a Pd-coated tube. Inorganic and organic species of As were determined in freshwaters by similar methodology after separ- ation by ion chromatography (94/2198). The use of chelating resins to preconcentrate Pb from water samples prior to analysis is not uncommon (e.g. 94/275,94/560 94/566).Chikuma and Aoki (94/560) employed a resin based on a derivative of dithizone; a suspension of the Pb"-bearing resin was then introduced directly into an HG-AAS system. 2.1.4. Speciation In this review year there are a considerable number of papers which address elemental speciation in waters reflecting the growing awareness of the importance of this subject in assess- ments of environmental toxicity. Many of the studies on As Se and Sb speciation employ an HG-AAS detection step as listed in Table 2. 14 R Journal of Analytical Atomic Spectrometry February 1995 Vol. 10Table 2 SUMMARY OF WATER ANALYSES Technique; atomization; analyte form* Element Matrix Sample treatment/comments Reference 9412966 94/16 Preconcentration of dithiophosphoric acid 0,O- diethyl ester complex on C; desorption with HNO prior to determination (0.3 pg ml-') Speciation studies using ultrafiltration and dissociation kinetics; dissociation studies undertaken using ASV and Chelex - 100 exchange resin.Three A1 species with different dissociation rate constants identified in Rideau River water (pH 8). See also Cu 94/16 Preconcentration of lumogallion complex in the micellular phase of cationic and non-ionic surfactants prior to ultrafiltration through 10,000 molecular weight cut-off membranes. At pH 5.9 1 x M lumogallion and 2 x M cetyltrimethylammonium bromide gave quantitative retention at the pg ml-' level reported AsV reduced to As"' using KI (0.3 ng ml-') (As"'-NaOH-KI) in a FI system; generated species absorbed on a Pd-coated graphite furnace prior to analysis ( 15 ng ml - ) Coprecipitation with Zr (OH),; precipitate dissolved with HCl prior to analysis using Zr-coated graphite tubes Hydride generated with tetrahydroborate (111) immobilized on anion-exchange resin; hydride separated from solution with a gas-liquid separator prior to determination Review of methods and results for speciation Reduction using NaBH,; collection of arsine in a Comparison of methods; no significant differences FI introduction of NaBH hydride generated species; Arsine generated by the Fleitmann reaction cold-trap of Chromosorb WAW-DMCS at liquid N temperature On-line GC separation of hydride species Review of applications for speciation using Removal of spectral interferences using a .chromatographic separation Dowex - 1x8 anion-exchange resin; elimination of ArC1' interference at 75 and 77 u Review of hydride generation techniques Separation of AsV As"' monomethylarsenate and dimethylarsinate using an Y SA-I1 anion-exchange column followed by reduction with KBH prior to determination (0.2-0.8 ng ml-I) dimethylarsinate arsenobetaine and arsenocholine.Use of anion-exchange HPLC coupled to an on-line thermo-oxidation unit prior to Speciation of AsV As"' monomethylarsenate HG-AAS Sensitive determination of the chemical warfare agent Lewisite (2-chlorovinyl dichloro arsine) Speciation studies using ion chromatography and off- line HG hydrides preconcentrated on a Pd-coated graphite tube. AS"' AsV arsenobetaine monomethylarsenate dimethylarsenite p-aminophenylarsenate and arsenocholine separated using a NH,H,PO mobile phase at pH 5.8 on anion- and CASl ion-exchange columns connected in series (1.6-1.9 ng ml-') Survey of species in west Pacific Ocean On-line reduction of As"' to AsV using HCI Continuous FI-HG system; study of matrix effects (0.02 ng ml - ') Ag Sea and river water AA;ETA;L A1 Natural water AA;ETA;L A1 Water 941 17 A1 As As Drinking water Water Water AA;-;L AA;Hy;L AA; ETA; L 941538 941238 941283 As Natural water AA;ETA;L 94/30 1 As River water AAHy;L 941350 As As Natural water Sea-water AA ; H y ; L AA;quartz-cell HY;L 94/48 1 941482 As As Water Water AA;Hy;L AA;-;L 94/48 5 941492 As Sea-water MS;ICP;L 9416 13 As As Water Natural water AE;Hy;L AA;-;L 9411040 9411 626 As Water AA;Hy;L 9411640 As Water As Water AE;MIP;L AA;ETA Hy;L 94/C 1 9 6 3 9412198 As Sea-water As Po table water As Mineral water MS;ICP Hy;L AA;Hy;L AA;ETA Hy;L AA;silica tube Hy;L AA;Hy;L 9412707 9412891 9412925 As Water Speciation studies using on-line microwave oxidation followed by HPLC separation (0.3-0.9 ng) Preconcentration on a mercaptoacetamide resin Preconcentration using FI microcolumns of Amberlyst A-26 and sulfhydryl cotton ( 1 ngml-') HN03 to pH 2 before determination (0.02 pg ml-') Sample treated with CaCl solution acidifed with 9412926 Au Water Au Water AA;-;L AE;ICP;L 941209 941568 AA; ETA;L B Water 94/69 1 15R Journal of Analytical Atomic Spectrometry February 1995 Vol.10Table 2 (continued) Technique; atomization; analyte form* AA;ETA;L Sample treatment/comments Analysis of drinking water from 89 sites in Italy; Zeeman and continuum source background correction compared Solvent extraction using 2-thenoyltrifluoroacetone Direct detemination of trace levels using an intracavity laser spectrosopic method (0.2 pg m1-I) Element Ba Ba Ba Be Be Cd Cd Cd Cd Cd Cd Cd Cd Cd Chloride Chlorine c o Cr Matrix Potable water Reference 941893 9411 025 9412929 River water Water AE;ICP;L AA molecular absorption;intra- cavity 1aser;L AA;ETA;L l'reconcentration of acetylacetanoate complex on activated carbon at pH 8-10; suspension of adsorbed complex introduced directly into furnace (0.6 pg ml;') phosphomolybdate and ascorbic acid (0.03 ng ml-') (Cryptand 2.2.1) C18 micro-column; species eluted with MeOH (0.2 pg ml-l) Sequential metal vapour elution analysis using a heated Mo capillary column (1-15 pg m1-I) Vapour generation using sodium tetraethylborate; application to potable water and SRM 1643c (20 pg ml-') cathode placed in furnace and heating cycle initiated (0.01 ng ml-') Study of concentrations in Antarctica during the past 155 000 years Separation using anion exchange of chloro-complexes (0.13-0.17 pg ml-') Solvent extraction using dithizone into hexane followed by back-extraction with HN03 Continuous flow generation of volatile species using NaBEt (0.4 ng m1-l) Indirect determination based on monitoring of Ag (2.3 pg ml-I) Analytical procedure for measurement of stable isotopes with precision sufficient for geological and hydrological studies E'reconcentration using nitroso R; filtrate collected on a cellulose nitrate membrane dissolved in DMF and analysed ( 5 pg ml- ') 8-hydroxyquinoline complex into IBMK.Effects of pH extraction and heating time and amounts of extraction reagents investigated (4 x 90 pL) onto a pyrocoated graphite tube (0.057 ng m1-I) On-line separation of Cr"' using a IC 7000s column (75 pg ml-') On-line separation using an automated system for Cr'" and CrV1 determination (0.5 ng ml-') Co-precipitation of CrV1 with AgCl at pH 8-9; precipitate floated by addition of a 1 + 1 mixture of sodium dodecyl sulfate and sodium oleate and bubbling N,. Precipitate filtered on micropore glass filter and dissolved with NH diethyldithiocarbamate at pH 3.5; total Cr by oxidation of Cr"' with KMnO prior to co-precipitation (19 ng) co-precipitated using Ga(OH) at pH 8.9-9.4; total Cr determined after reduction with hydroxylammonium chloride alumina column; CrV1 retained at pH 2.0 and Cr"' at pH 7.0 S1:paration of Cr"' and Crvl using a strong basic ion- exchange resin; use of a mixed elution system of ascorbic acid and sulfuric acid ng m1-l) Matrix modification using ammonium l'reconcentration using a macrobicyclic polyether l'reconcentration of APDC complexes on a silica gel Electrodeposition on to a three coil W wire cathode; Bxtraction of Cr"' and CrV' using 0.1 mol 1-' Ilu-situ preconcentration by multiple injections Co-precipitation of CrV' using zinc Speciation of Cr"' and CrV1.Cr"' selectively 94/c 193 1 Speciation studies using selective retention on a 94lC1937 9412640 Matrix modification using V and V-Mo (0.2 9412934 9419 Sea- and rain water AA;ETA;L 941856 Drinking water AA;-;L AA;ETA;L 94/83 941226 Water Sea-water 941328 941582 River water Water AA;-;L AF;H y;L 941664 River water A A;ETA;L 9411736 941 1 744 9412133 94/29 15 9417 1 9 94/22 3 7 Ice and Snow Surface water Sea-water Water Natural water Brines and aquifers AF;laser;L AA;-;L AA;-;L AE;ICP;L AA;F;L -;-;L River water A A;ETA; L 9411 1 1 8 941262 Water AA;ETA;L AA;ETA;L 9411084 Cr Cr Cr Cr Sea-water Water Drinking water Water MS;ICPL AA;F;L AA;ETA;L 9411423 9411605 9411 717 AA;ETA;L 9411 8 3 1 Cr Natural water Cr Sea-water AA;ETA;L AA;F;L Cr Cr Cr Water Waste water Lake water AA;-;L AA;ETA;L 16R Journal of Analytical Atomic Spectrometry February 1995 Vol.10Table 2 (continued) Technique; atomization; analyte form* Element Matrix Sample treatment/comments Reference c u Natural water AA;ETA,L Speciation studies using ultrafiltration and dissociation kinetics; dissociation studies undertaken using ASV and Chelex - 100 exchange resin.Four Cu species were identified according to their dissociation rate constants. See also Al 94/16 Preconcentration of APDC complexes on a silica gel CIS micro-column; species eluted with CH,OH (0.2 pg ml-l) On-line FI solvent extraction; sample pH adjusted to 7 and merged with a 0.1 YO solution of 5,7-dibromo-8-hydroxyquinoline in xylene. Mixture extracted and organic phase nebulized. Effects of pH flow rate extraction coil length and configuration loading time concentration of ligand and ultrasonic agitation on the signal intensity investigated Determination of leaching from antifouling coatings; solvent extraction using diethyldithiocarbamate of leachate Survey of species in west Pacific Ocean.See also As ref. 9412707 Direct nebulization of sample containing 1 % SnCl in 1% HCI into pneumatic nebulizer; increase in sensitivity noted on the introduction of the reductant (1.3 ng ml-') organomercury species (0.1 pg ml-') CV generated species (628 fg m1-l) with a microcolumn of sulfhydryl cotton 9411 6 941226 941253 Simplified approach for on- and off-line oxidation of In-situ concentration on a Pd-coated graphite tube of Preconcentration of Hg species using a FI manifold (6 Pg m1-'1 Reduction with NaBH and SnC1 in acidic solution; no interference from iodide noted c u c u Sea-water Water AA;ETA;L AA;F;L c u Sea-water AA;-;L 9412 102 Ge Hg Sea-water Waste water MS;ICP Hy;L AE;ICP;L 9412707 94/75 Water Water Natural water AA;-;L AA;ETA CV;L AF;CV;L 941225 94/24 1 941327 Natural water AA; CV;L 941348 Water AA; CV;L Preconcentration using a cellulose-hyphan ion exchange resin prior to cold vapour generation See As 941492 Generated species trapped on a Au coated graphite Comparison of techniques; accuracy assessed by tube prior to determination (0.8 pg rn1-l) analysis of CRM ORMS-1 941355 Water Water AA;-;L AA;ETA Hy;L 941492 941720 Water A A;CV L AE;MIP;L AF;-;L AA;CV;L 941765 Water Effects of bromide bromate iodide iodate periodate sulfide sulfite and thiosulphate in acidic and basic media studied Preconcentration using xanthate cotton followed by dissolution with aqua regia reduction and analysis ID analysis using an enriched spike of 201Hg (0.2 pg ml-') Active microbial preconcentration and reduction using Aeromonas hydrophilia HGS 2 Improvements in CV technique reported by incorporation of on-line membrane dryer for elimination of water vapour.Addition of organized media micelles or vesicles improved the kinetics of volatile species generation; didodecyldimethylammonium bromide gave the best results (0.2 ng ml-') preconcentration using a FI system with a microcolumn of dithiocarbamate resin (0.05-0.15 pg ml-') Use of 0.6 YO NaBH and 8% HC1 for reduction of sample (0.1 1 ng ml - I ) Direct detemination of trace levels using an intracavity laser spectrosopic method (0.15 pg ml-I). See also Ba ref. 9412929 complex generated by heating determinand and Hg in graphite furnace (3.0 ng ml- ') Speciation studies using coupled GC; 9412 2 5 6 9412 730 9412929 Indirect determination of I as an HgJ complex; 9412958 Higher sensitivities than an C,H,-air flame reported 9414 15 9411088 9411161 9411283 9411733 9412200 Water Natural water Waste water Sea-water AA;CV;L MS;ICP;L AA;-;L AA;CV;L AE;ICP CV;L Hg Natural water AE;MIP;L Hg Waste water I Water AA;CV;L AA molecular absorp tion;in tra- cavity 1aser;L AA;ETA;L I Po table water K Water K Ground water LEI;F C2H,-air-Ar;L AA;F,air-C,H,;L Acidified sample filtered prior to determination 9412291 (pgm1-l) Journal of Analytical Atomic Spectrometry February 1995 Vol.10 17 RTable 2 (continued) Technique; atomization; analyte form* AE;ICP;L Matrix Natural water Sample treatment/comments Reference 9411775 941559 FI on-line preconcentration using a miniature column of CL-P507 resin (0.7 ng ml-I) Interference effects from a sea-water matrix investigated; elimination using ascorbic acid (0.12 ng ml-') of sample and the use of an internal standard required to correct for signal suppression; polyatomic interferences from BrO' and BrOH' reduced by matrix matching (pg ml-I).See also K ref. 94/2297 (0.6 pg ml-I) accuracy assessed by analysis of CRM CASS-1 Preconcentration using a chelating resin based on a derivative of dithizone; suspension of metal- adsorbed resin introduced into hydride generator Preconcentration using Chelex-100; accuracy of isotope ratio determination verified by analysis of CRM NASS-3 and SRM 981 (0.8 pg ml-') and trap GC-MS after ethylation extracted derivatized by propylation using a Grignard reagent and analysed by directly coupled Determination in a candidate RM.Ten-fold dilution 9411322 Acidified sample filtered prior to determination Preconcentration using a Nafion-modified electrode Preconcentration using Chelex-100 and HG (6 P g m w Determination of isotope ratios in sample by purge Speciation of organolead compounds. Sample GC-MIP Speciation studies near a battery recycling plant in China; Pb preferentially accumulated in the exchangeable and carbonate fraction Computer simulation of Pb speciation Direct determination using a known addition method; no separation 1 concentration steps or matrix modification required. Analysis of 4 NRCC CRMs (1 pg m1-l) introduction by either nebulization or ETV (0.3-0.8 pg ml-l) solvent extraction of the phosphoantimonyl molybdate complex into IBMK Preconcentration using activated charcoal; sample Comparison of methods.Direct nebulization versus See also Au 941209 Distribution and behaviour in waters of the Tulameen ultramafic complex British Columbia Canada studied introduction by either nebulization or ETV (0.3-0.8 pg ml-'). See also Pd ref. 9412195 Matrix modification using ascorbic acid (0.27 ng m1-I) Indirect determination based on the reaction of covalent hydride with mercury Extraction of Sb"' and SbV using APDC into IBMK investigated (2 ng m1-l) On-line preconcentration using a microcolumn packed with 8-hydroxyquinolime immobilized on controlled pore glass.Determinand eluted with 4 moll-' HC1 directly into hydride generator (1.5 pg m1-I) extraction with lactic acid - malachite green and a FI - hydride system. The former was the preferred method followed by ETAAS phosphate kinase immobilized on controlled pore glass ;Study of distribution and pattern of Sb circulation in Italian spring water (< 1 ng rn1-l) FI introduction of NaBH hydride generated species; SeV' reduced to Se" using 6-8 mol 1-' HCl (0.3 ng ml-I). See also As ref. 941238 Preconcentration using activated charcoal; sample Comparison of methods for Sb speciation; selective Selective separation of Sb"' using fructose-6- :See As ref. 941613 El em ent La Mn Mo River and sea-water AA;ETA;L MS;ICP:L Sea-water Na Pb Pb Ground water Water Sea-water AA,F,air-C,H,;L AA;ETA;L AE;ICP Hy;L 9412297 941186 941275 AAHy;L 941560 Pb Natural water MS;ICP;L 941566 Pb Sea-water Pb Pb Sea-water Snow MS;-;L AE;MIP;L 941 1 48 6 941 1 604 AA;-;L 9411786 Pb Water Pb Pb Water Sea-water -;-;L laser excited AF;ETA;L 941c2025 941293 1 Pd Fresh water MS;ICP;L 9412195 Phosphonate Brine AE;ICP;L AEDCP;L 941493 AA;-$ -;ICP;L Pt Water Pt Water 941209 941864 MS;ICP;L Pt Fresh water 94/21 95 Ru Water Sb Water Sb Water Sb Water AA;ETA;L AF;Hy;L AA;F slotted tube atom trap;L AA;Hy;L 9412889 94/25 94/26 1 941376 Sb Natural water A A;ETA,L 94/49 1 AA;ETA;L Sb Water 941585 Sb S e Water Water AA;ETA;L AA;H y;L 941795 94/238 Se Sea-water MS;ICP;L 9416 1 3 18R Journal of Analytical Atomic Spectrometry February 1995 Vol.10Table 2 (continued) Technique; atomization; analyte form* A A;ETA;L Element Se Se Se Si Sn Sn Sn Sn Sn Sn Sn Sn Sn Sn Sn Sn Sr Tc T1 U U U Zn Zn Zn Various (6) Matrix Drinking water Sample treatment/comments Reference 9411785 9412196 9412925 941465 94/27 1 941485 941487 941707 941775 941 1 03 0 9411812 9411 828 9412 1 50 9412210 941228 1 9412586 9411390 941 148 5 9411223 9412 17 9412234 9412428 9411 165 9411 744 9412957 94/22 94/44 94/45 94/54 I Q R Matrix modification using either Ni or Ni + Pd nitrates; the latter gave improved sensitivity (0.73 ng ml-') Optimization of operating conditions (2.5 pg ml-') Continuous FI - HG system; study of matrix effects (0.02 ng ml-').See also As ref. 9412925 Sea-water Mineral water MS;ICP Hy;L AA;ETA Hy;L AA;silica tube HY;L A A;ETA;L Mineral water Determination using Ca-based matrix modifier and a W-coated graphite tube Graphite furnace analysis using either Mg + HNO or Pd+Mg as modifier (0.97 and 1.64 ng ml-') See As ref.941485 Preconcentration of sodium diethyldithiocarbamate complexes using rotary evaporation followed by Grignard derivatization prior to on-line GC separation Preconcentration of ionic organotin compounds on Cl8 column followed by on-column ethylation using Na tetraethylborate. Eluted species separated by GC prior to determination (pg ml-') On-line packed column GC (0.35 pg ml-') Tap water AA,ETA,L Natural water Water AA;Hy;L AA;-;L Water AEMIPL Water Natural water AAquartz AA;ETA;L furnace;L Coprecipitation using gallium phosphate at pH 3; Hafnium-impregnated graphite tube used (0.23 ng m1-I) Alkyltin speciation using on-line hydride generation with GC; sample clean-up using SPE (0.5 pg) Sample cleanup of organotin species using SPE Peralkylation of species followed by GC separation; study of levels and distribution in the River Elbe Germany Solvent extraction using toluene followed by ETAAS with Zeeman background correction (40 pg ml-') Preconcentration using a TOPO-coated W probe; no interferences noted from a range of cations and anions (0.4 ng ml- ') Speciation studies of butyl- and phenyl-tin species by GC-MIP-AES (0.1 pg ml - I) Separation by double ion-exchange procedure; determination of isotopic composition Chemical separation to remove mass and matrix interferences; comparable detection limits with those obtained with radiometric methods Use of pyrolytcally-coated graphite tube and PdClz modifier (0.68 ng ml-') Preconcentration on Fe 2,2,4-trimethylpentyI methylphosphonate (0.06 ng ml- ') Dissolved U from 250 samples from the Orinoco Amazon and Ganges basins reported; use of ID analysis using 235U as the enriched spike Determination at low concentration Sample evaporated prior to analysis (0.005-0.025 pg m1-l) Separation using anion exchange of chloro-complexes (0.99-2.97 pg ml-').See also Cd ref. 9411744 Direct determination with Zeeman background correction; effects of chemical and spectral interferences studied (60 pg ml-') Preconcentration using immobilized 8-quinolinol on either CAPCELL-NH (silicone-coated silica gel with alkyl amino groups) and SEPABEADS (polyvinyl polymer with alkyl amino groups).Determinations of metals (Cd Cu Fe Ni Pb and Zn) in NASS-3 were in agreement with certificate values Preconcentration of Na dibenzyldithiocarbamate complex by reversed phase HPLC; study of water from four deep-water stations in the Atlantic Ocean (Cu Mn Ni Pb Se and Zn) Certification of a BCR reference material (CRM 403). See also Various 94/44 for preconcentration details (Co Cu Fe Mn Ni Pb U V and Zn) Preconcentration on cartridges packed with iminodiacetic acid modified silica (Cd Co Cu Fe Mn Ni Pb and Zn) Sea-water Sea-water River water AE;MIPL AA;-;L AA;-;L A A;ETA;L AA;ETA;L Waste water Drinking water Water Brine water Sea-water AE;MIP;L MS;-;L M S;ICP;L Water Water River water AA;ETA;L XRF;Pd anode;L M S;ICP;L Water Potable water TXRF;- ;L AA;F air-C2H,;L Surface water AA;-;L Sea-water AAETA;L Sea-water AA;ETA;L MS;ICP;L Various (6) Sea-water TXRF;-;L Various (9) Sea-water Various ( 8 ) Natural water TXRF;-;L AA;-;L Journal of Analytical Atomic Spectrometry February i995 Vol.10Table 2 (continued) Technique; atomization; analyte form* AA;F;L AA;ETA;L AA,H y;L XRF;-;L AE;ICP;L AE;ICP;L AA,F;L EDXRF;-;L AA;-;L Element Various (6) Various (4) Various (8) Various Various (3) Various (6) Various (12) Various (3) Matrix Water Drinking water Wastewater Waste water Mineral water Water Water Sea-water Sample treatment1comments IOptimization of system; study of matrix effects Survey of bottled drinking water sold in Canada (Al Review of technique for batch and continuous HG Primary screening of industrial wastewater As Cd and Pb) (As Bi Ge Pb Sb Se Sn and Te) k ference 94/86 941128 941143 941 144 941161 94/188 94/23 1 941234 Preconcentration of thiocarbamate complexes on ion- exchange resin (Co Mo and V) (On-line FI preconcentration using ion exchange (0.2-5 ng ml-') (Cd Cu Mn Ni Pb and Zn) ICoprecipitation with Al(OH) at pH 7.3 Preconcentration using Chelex-100 and Lewatit TP 207; comparison of the two resins indicated that the latter is able to recover both the colloidal form and the dissolved free ionic form of Cr"' (Cr Cu and Mn) Preconcentration using Chelamine chelating resin; accuracy assessed by analysis of marine CRM CASS-2 (Cd Cu Mn Ni Pb and Zn) Simultaneous determination of 8 trace elements (Cd Co Cu Fe Mn Ni Pb and Zn) after chelation preconcentration on a MetPac CC-1 column (1.6 pg ml-' to 55 pg ml-') Review of applications Preconcentration of 8-hydroxyquinoline and Bismuthiol I1 metal complexes and ion-association complexes of 8-hydroxyquinolinol-5-sulfonic acid with tetrabutylammonium on a poly(chlorotrifluoroethy1ene) resin Review of FI systems for sea-water analysis Abridged version of EPA method 60014-91-010 for the determination of metals in environmental waters Lac Sheen Cu-Ni-PGE occurrence in Quebec Canada Preconcentration using modified silica sorbents (0.25-24 ng m1-l) :Sorption-preconcentration of colloid particulates and organometallic complexes on macroporous DEAE sorbents Review of methods used by MAFF for the speciation of organometallic compounds Preconcentration using a chealting poly(dithi0carbamate) resin with macroreticular support (Cu Fe and Zn) Ion-line preconcentration using 8-hydroxyquinoline immobilized on controlled pore glass.Optimum conditions determined for each element (3 ng m1-l) (Al Ga and In) .4pplication of TXF for sea-water analysis in the North Sea research projects ZISCH and PRISMA Direct determination of river water; estuarine water required separation and concentration by complexation with Na dibenzyldithiocarbamate and reversed-phase HPLC (1-3 ng ml-') 'Trace element deposition in a forest ecosystem studied Evaluation of instruments; 16 elements determined (1 ng ml-') Sample filtered and concentrated using a rotary evaporator prior to analysis Preconcentration using a liquid membrane emulsion (Span 80 2-ethylhexyl phosphoric acid mono-2- ethyl hexylester and di-2-ethylhexyl phosphoric acid kerosene in 1 mol I-' HC1 and 0.02 moll-' H,SO,) (Cd Co Cu Fe Mn Ni Pb and Zn) :Direct analysis using Zeeman background correction Mineral waters (96 samples) analysed by Zeeman Study of heavy metal transport in a river system in !Feasibility study for the monitoring of metals in wet 'Transport and fixation of Au Pd and Pt around the background correction Brazil deposition at 3 sites Various (6) Sea-water Various (8) Sea-water AA;-;L MS;ICP;L 941240 941 290 Various Various Water Tap water AF;-;L AA,F;L 941342 941346 Various Sea-water Various Natural water --;L AE;ICPL MS;ICP;L 9413 8 3 9414 1 3 AA;ETA;L Various Natural water 941435 AA,-;L AA;-;L Various Water Various Surface water 941458 941459 AA;-;L AA;F;L Various Natural water Various (3) Natural water 941480 941495 Various (3) Natural water AA;F;L 941553 Various Sea-water Various River water TXRF;-;L TXRF;-;L 941655 941657 Various Rain water Various Pure water Various (12) Rain water Various (8) Potable water TXRF;-;L 941658 941695 9417 15 941730 laser-induced AE;ICP;L AF;MIP ETA;L AA,-;L Various Natural water Various Mineral water 941796 941797 AA;ETA;L AA;ETA;L Various River water AA;-;L 9418 3 1 Various Rain water MS;ICP;L AF;CV;L 941841 20 R Journal of Analytical Atomic Spectrometry February 1995 VoE.10Table 2 (continued) Technique; atomization; analyte form* AE;ICP;L MS;ICP;L XRF;-;L AA;-;L AA;-;L Element Various Various Various (3) Various (6) Various (9) Matrix Sea-water Sample treatment/comments Review of techniques used for sea-water analysis Reference 94/896 9411021 9411028 9411033 Natural water Preconcentration of MnO,- Cr04'- and using a cellulose ion-exchange resin (Hyphan).Effect of pH on distribution coefficients studied Use of STPF conditions with matrix modification and Zeeman background correction (As Hg and Se) (5-10 ng ml-l) Preconcentration using an amidoxime resin. Resin prepared by the aminolysis of acrylonitril- divinylbenzene coploymer with hydroxylamine (Cd Cr Cu Ni Pb and Zn) Coprecipitation with hydrated MnOz (0.02-2.2 ng ml-') (As Bi Co Fe Mo Pb Sb Sn and V) Coprecipitation using cerous hydroxide; precipitate floated by addition of surfactant (sodium oleate) and bubbling of N2. After collection precipitate dissolved in HNO prior to determination (Cd Cu Fe Mn Pb and Pd) Critical evaluation of a multielement ETAAS system using line sources and a transversely heated graphite atomizer with Zeman effect background correction (Cd Cu and Pb) On-line preconcentration using quinolin-8-01 immobilized on silica at pH 8 (7-130 pg ml- ') Preconcentration using a DETATA filter containing aminocarboxylic groups; filter dried and analysed (1-3 ngml-') Use of ultrasonic nebulizer for improved sensitivity Preconcentration using cotton cellulose xanthate at pH 7 (Cu Pb and Zn) Cryogenic desolvation and addition of Hz to aerosol gas enhanced determinant signals by 2-3 times while reducing polyatomic interferences from C10+ CaO' and ArCl' (As Ni and V) Preconcentration using fusible agents based on higher carboxylic acids (C1,-Cz0) (Cd Cu Pb and Zn) Matrix modification using a mixture of ammonium oxalate and tetraamminepalladium (11) chloride Automated on-line preconcentration of APDC complexes on a C18 microcolumn Preconcentration using adsorbent cotton at pH Sampling and analysis of groundwater from 17 wells in Saudia Arabia Acidified sample analysed after microwave digestion in a closed vessel; environmental study of Elbe River system procedures outlined Sb) (0.01-0.001 pg ml-') in India reported collection filtration and analysis analysis exchange resin investigation of appropriate matrix modifier (As Cd Pb Se and Zn) Separation using a Chelex- 100 impregnated silica CI8 resin; matrix modification using Pd(NO,),-Mg( NO& and Zeeman background correction determiantion of trace heavy metals in surface samples of Arctic snow.Accuracy assessed by analysis of NRCC SLRS-2 (fg) Study of ETV-MIP-AAS system 6.5-7.0 Automated collection sampling and analysis Analysis of environmental samples (As Bi Hg and Trace metal levels in water samples from 55 locations Protocol for minimizing contamination during Evaporation of sample on spectrally pure C prior to Field portable instrument; preconcentration using ion Simultaneous multielement analysis of 4 elements; Application of ETV-ICP-MS for the direct Sea-water AA;ETA;L Natural water AA;-;L 9411 044 94J1089 AA;-;L AA,F;L Natural water Sea-w ater Various Various Various Various Various Various Various Sea-water AA;ETAL 9411 184 Natural water Water MS;ICP;L XRF;-;L 9411 194 9411 199 Drinking water Natural water AE;ICP;L AA;F air-CzHz;L 9411247 941 1 260 Sea-water MS;ICPL 9411281 Various (4) Natural water 9411 602 XRF;-;L Various Sea-water Various Sea-water Various Water Various Natural water Various Natural water AA;ETAL AA;ETA;L 941161 1 9411616 9411624 9411 692 9411 723 9411 762 9411787 9411 796 9411 8 1 6 9411 8 3 3 941C1894 94lC1947 Various Rain water Various (4) Natural water Various Drinking water Various Lake water Various Natural water Various Water Various ( 5 ) Waste water _ _ ; ;L AE;ICP Hy;L AA;-;L -*-;L AE;arc discharge;L XRF;-;L AA;ETA;L Various Sea water AA;ETA;L 94/207 1 9412194 Various (10) Snow Various Water MSICP,ETV;L AA;MIP,ETV;L 94/2 199 Journal of Analytical Atomic Spectrometry February 1995 Vol.10 21 RTable 2 (continued) Technique; atomization; analyte form* AE;ICP;L Element Matrix Various (6) Rain water Sample treatment/comments Reference Preconcentration using Chelex-100 at pH 6 followed 9412292 Coprecipitation using Mg( + NaOH; 9412298 by elution with HNO (0.1-10 pg ml-') precipitate centrifuged and dissolved in HNO (3.5-16.7 ng ml-') Improved optical system using Roentgen optics cut- 9412454 off filter Survey of ground water in India 9412497 Preconcentration using an 8-hydroxyquinoline 9412537 On-line preconcentration of butane-2,3-dione 94/25 3 8 chelating resin (0.02-0.4 pg ml-') bis( N-pyridinoacetyl hydrazone) metal complexes on an Amberlite XAD-4 resin at pH 8-9 (Cd Co Cu Ni and Pb) extraction of APDC complex into CHCl pH 7.5; use of Dowex 50 a cation-exchange resin pH 5.2; and evaporation of acidifed sample.Close agreement between results by each method CM-cellulose (carboxymethylcellulose 8-hydroxy- 5-sulfo-7-quinyl ester). Effects of pH column capacity and eluent composition studied (0.3-2 pg ml-') In-situ preconcentration on a pyrolytically coated graphite tube; use of multiple injections (3-9 pg mi-') (Co Cr Cu Fe Mn and Ni) SRM 1643b used for quality control for first row transition elements Comparison of preconcentration methods. Solvent On-line preconcentration on SO,-oxine Assay of 100 samples from the former USSR; NIST Use of ultrasonic nebulizer and a high resolution MS FI-ID analysis; analysis of RMs Multi-element speciation using Chelex- 100 Sep-Pak C and Fractogel DEAE. Method distinguishes between labile complexes non-polar organic adsorbable matter and ion exchangeable substances Comparison between two techniques; analysis of samples from deep ground waters from Gorleben Germany.Precision and detection limits of ICP-MS superior from BCR efficiency and recovery monitored 9412851 Application of technique for the certification of RMs Preconcentration using Dowex cation exchange resin; 9412906 94/29 17 Various Natural water AA;F;L XRF;-;L Various Water Various Ground water Various Sea-water XRF;Mo anode;L MS;ICP;L Various ( 5 ) Water MS;ICP;L Various Surface water A A; E TA;L 9412546 Various Water MS;ICP;L 9412585 Various (6) Water A A;ETA;L 9412697 Various Natural water MS;ICP;L 9412 69 8 Various Terrestrial water MS;ICP;L 9412793 Various Various (10) Fresh water MS;ICP;L MS;ICP;L 941281 1 94/28 12 Various Ground water MS;ICP;L NAA;-;L Various Water MS;ICP;L AE;ICP;L Various Mineral water (REE) * Hy indicates hydride and S L G and S1 signify solid liquid gaseous or slurry sample introduction respectively.Other abbreviations are listed elsewhere. t Values in parentheses are detection limits. Methods designed to isolate the individual ionic species are more varied although HPLC separation seems to be increas- ingly popular when both organic and inorganic As species are required (94/492,94/1640 94/2926). In one study the chroma- tographic overlap of arsenite and arsenobetaine was overcome by a novel coupling of anionic cartridges to an HPLC column (94/2926). Other methods reported have employed ion chroma- tography (94/1626 94/2198) and collection in a cold-trap of Chromosorb WAW-DMCS (94/482).In another method As"' and AsV were coprecipitated with zirconium hydroxide the precipitate dissolved in HCl and the solution injected into a Zr-coated graphite tube (94/301). By means of different temperature programmes As"' was quantitatively removed while AsV remained in the furnace up to a temperature of 1400°C. Preliminary work on an enzymic method for the speciation of Sb"' and SbV based on the enzyme fructose-6-phosphate kinase followed by ETAAS has been reported by a group of Spanish workers (94/585 j. The enzyme immobilized on con- trolled-pore glass packed in a glass microcolumn selectively separates and preconcentrates Sb'" which is an advantage as this species occurs at lower concentrations in the environment than SbV.However more method development is required to obtain full recovery of the Sb"'. Studies of organotin speciation have continued unabated with many variations on analytical schemes involving separ- ation by GC coupled with detection by AAS or AES (94/485 94/487 94/775 94/1812 94/2150 94/2586 94/2810j. A semi- automated FI system has been developed for on-line precon- centration of ionic organotin compounds from river waters (94/707). Sorption on bonded silica with octadecyl functional groups was followed by co-column ethylation with sodium tetraethylborate. The derivatized species were eluted with methanol separated by GC and detected by MIP-AES; an LOD of 0.1 ng 1-' was achieved. The determination of chromium species in aqueous solution has stimulated a variety of analytical approaches including the separation of the Cr species as their EDTA complexes by ion chromatography prior to analysis by ICP-MS (94/1423).Yehl et al. (94/C1937) critically evaluated the method of Sperling et al. based on the selective retention of either Cr"' or CrV' on alumina. They highlighted some critical steps in 22 R Journal of Analytical Atomic Spectrometry February 1995 Vol. 10the procedure and the susceptibility of the CrV' separation to interference from sulphate. A useful compilation of methods for the analysis of organometallic species has been published by a UK laboratory which has considerable experience in this area of work (94/480). It includes their current practices for the determination of Hg Sn As and Pb organo-species. 2.2.Instrumental Analysis 2.2.1. Atomic absorption spectrometry Flame atomic absorption spectrometry still has an important niche worldwide as indicated by the number of entries for FAAS in Table2. However for this mature technique where the main effort is directed towards the development of precon- centration strategies to improve the LODs there is little new to report. An unusual method involved the determination of Cd in river water by sequential metal vapour elution analysis in which Cd vapour is separated from those of Ca Fe and Na in a molybdenum capillary tube heated to 1760°C prior to FAAS (94/328). Ways of overcoming the substantial matrix effects encoun- tered when determining trace element concentrations in sea- water by ETAAS continue to evolve. Several authors employed a combination of Zeeman-effect background correction together with specific matrix modifiers for the elements of interest i.e.As Hg and Se (94/1028) Cd Mn and Pb (94/1611) Cu Cd and Pb (94/2071) and Zn (94/2957). One of these studies investigated the microdistribution of palladium on Pd-conditioned graphite platforms and its affect on the subsequent analysis (94/1611). Duan et al. (94/2199) designed an ETV device to introduce an aerosol directly into an MIP coupled to an AA spectrometer and applied it to the analysis of waters. They reported a relatively reduced matrix effect and higher tolerance to con- comitant elements compared with MIP-AES as well as a smaller effect from EIEs. Although the characteristic concen- trations for electrothermal MIP-AAS were comparable to or better than those for FAAS they were 1-2 orders of magnitude poorer than those by conventional ETAAS.Methods for the determination of iodide in waters are usually noteworthy because they are relatively rare. Bermejo-Barrera et al. (94/2958) devised an indirect method based on the measurement of a mercury signal generated when small amounts of an iodide-mercury complex are heated in a graphite furnace. The authors claim an LOD of 3 pg 1-' which would be suitable for many potable waters but they state that chloride fluoride and bromide ions interfere with the measure- ments. Surprisingly no details of the magnitude of these interferences are given making it difficult to assess whether the method is robust for practical analysis.2.2.2. Atomic emission Multielement analysis of waters by inductively coupled plasma atomic emission spectrometry continues steadily without any particularly new developments. It is widely recognized that improvements in LODs of about an order of magnitude would suffice for many applications. Improved performance figures obtained by ultrasonic nebulization were cited by two instru- ment manufacturers (94/1130 94/1247). Although this sample introduction technique enhances transport efficiency for a wide range of elements it elevates the concentration of all the elements present and is not suitable for saline matrices. Therefore Jendricke and Brauner (94/1130) suggest that for the analysis of sea-water an alternative approach is to separate and preconcentrate trace elements by chelation on a column of a cellulose derivative.Table 2 gives details of other strategies adopted including separation and preconcentration by ion- exchange when determining low concentrations of Co Mo and V (94/161) and REE (94/2917) in mineral waters or Al Cd Cu Mn Pb and Zn in rainwater (94/2291). The disadvantage of many of these methods is that they are by their very nature selective and therefore do not fully utilize the multielement capability of ICP-AES. Vapour generation is another means of improving analytical sensitivity; an impressive LOD of 6 ng 1-' for Pb in sea-water was obtained by a combination of chelating resin preconcen- tration followed by HG-ICP-AES (94/275 94/1787). One of the more novel variants on this theme used sodium tetra- ethylborate to generate volatile alkylated Cd species which were introduced into an ICP-AES instrument from a continu- ous vapour generation system (94/2915).The nature of the volatile compound formed has yet to be positively confirmed but the reported LOD of 0.4 ng ml-' for the determination of Cd in a sea-water matrix sounds encouraging. Speciation analysis of organolead compounds in snow at thefg g-' level is a very demanding proposition. Lobinski et al. (94/1604) have described a scheme for this analysis which involves preconcentration in a single step extraction derivatiz- ation by propylation using a Grignard reagent and determi- nation of the Pb species by microwave-induced plasma atomic emission spectrometry after further on-line preconcentration.Tri- and diethyllead species were the only compounds found in the majority of snow samples from Greenland. Capillary GC coupled to MIP-AES was employed to speciate Hg in natural waters after preconcentration using a dithiocarbamate resin micro-column installed in a closed FI system (94/2256). 2.2.3. X - Ray fluorescence Last year this writer noted her surprise at the paucity of new papers on total reflection X-ray fluorescence spectrometry. It is therefore pleasing to record a significant number of papers on this subject for the current review year even though the majority stem from one particular conference. The high sensi- tivity and multielement capability of TXRF with simple quantification using a single internal standard lends itself to the analysis of most types of natural waters including rain river and sea-water.Pepelinik et al. (94/658) give an analytical scheme for the analysis of rainwater by TXRF. Sulfur Ca and K were determined directly on a 25 pl aliquot spiked with cobalt as an internal standard whereas the trace elements were first concentrated by a factor of 20 by freeze-drying. Up to 25 elements were detected with LODs between 20 and 180 pg g-' after freeze-drying. The technique was also applied to the determination of 15 trace elements in dissolved and particulate fractions of river water (94/657). After filtration the particulate matter was digested with ultrapure nitric acid spiked with an internal standard and ultrasonically treated before XRF deter- mination on a quartz carrier.The preparation of the filtrate varied depending on the salinity of the waters; for estuarine samples the elements were separated and concentrated by complexation with sodium dibenzyldithiocarbamate and reversed-phase chromatography before XRF determination. LODs were between 0.05 and 0.5 pg 1-l for a 100 ml sample. TXRF has been applied to the difficult area of trace element analysis in sea-water with some success although to take full advantage of the high sensitivity of the technique it is necessary to separate the elements of interest from the bulk matrix. A group from Hamburg has been particularly active in this field (94/44 94/45 and 94/655). They contributed data obtained by TXRF for Co Cu Fe Mn Ni Pb V U and Zn at the nmol kg-' level to a certification exercise for a sea-water RM; their data compared favourably with those contributed by other techniques such as voltammetry AA and MS (94/45).The trace metals were preconcentrated and separated using sodium dibenzyldithiocarbamate and reversed-phase chroma- tography as in 94/657. This technique has been applied to Journal of Analytical Atomic Spectrometry February 1995 Vol. 10 23Rlarge research projects in the North Sea (94/655) and the Atlantic Ocean (94/44). Table 2 should be consulted for preconcentration methods for waters prior to determination by conventional XRF. These procedures include co-precipitation with aluminium hydroxide (94/23 1 ) filtration through a filter containing aminocarboxylic groups (94/1199) and preconcentration of U with iron 2,2,4-trimethylpentyl methylphosphonate (94/217).2.2.4. Mass spectrometry As the application of ICP-MS to the analysis of waters becomes more routine and the polyatomic interferences better under- stood workers are now seeking to demonstrate that the technique is sufficiently accurate and precise to be used for the certification of reference materials. Moens et aE. (94/2698) discuss the problems associated with the use of ICP-MS in certification work. While the technique is potentially accurate and precise this cannot be taken for granted; matrix effects and spectral interferences need to be rigorously studied and overcome for each sample type. An example of the caution necessary is the determination of Mo in a sea-water candidate RM (94/1322).Interferences on Mo isotopes were mainly attributed to BrO' and BrOH' ions; this was confirmed by separating Br from Mo by ion-exchange prior to analysis Considerable work has been and is still being performed to overcome the analytical difficulties of measuring arsenic and selenium in waters by ICP-MS. Goossens et al. (94/613) optim- ized an anion-exchange scheme based on Dowex-1x8 resin to separate As and Se from chloride which allowed deter- mination of As at m/z=75 and Se at m/z=77 in sea-water without interference from ArCl polyatomic ions. Hydride generation is another commonly used technique for effecting separation of these two determinands although in some of the reported applications of HG to ICP-MS a marked improve- ment in sensitivity has not been accompanied by a correspond- ing improvement in the LOD because the latter was blank limited.Tao et al. (94/2196) showed that careful cleaning of the HG apparatus the central tube of the ICP torch and the skimmer cone was necessary to obtain LODs of 2.5 pgml-' for Se and 0.3 pgml-' for As by HG-ICP-MS. Advances in automated sensitive methods of analysis par- ticularly ICP-MS has stimulated interest in examining the usefulness of lake and stream water in geochemical exploration surveys (94/864 94/2195). Hall and Pelchat (94/2195) deter- mined Pd and Pt by ICP-MS following preconcentration of the determinands by adsorption onto activated charcoal. Two modes of sample introduction were used direct nebulization and ETV; LODs were in the range 0.3-0.8 ng I-' for both elements with little difference between the two types of sample introduction.Application of this method to waters collected from various mineralized sites in Canada indicated that disper- sion patterns can be identified but maximum concentrations of soluble Pd and Pt were low and mainly <5 ng I-'. The same order of magnitude of dissolved Pt was also observed by Cook and Fletcher (94/864) who reported stream and bog waters containing < 1 ng I-' to a maximum of 2.5 ng 1-' Pt. The concentration of Pb in sea-water is increasing and Pb isotope ratios can help to elucidate its origin. Hitherto TIMS has been used for this purpose but a method with higher sample throughput would be advantageous for environmental studies. Miyazaki and Reimer (94/566) determined Pb isotopes in sea-water by a combination of chelating resin (Chelex-100) preconcentration and ICP-MS.The 206 204 208 204 207 208 and 206 208 Pb isotope ratios were measured with RSDs of 1.2 0.9 0.1 and 0.3% respectively. Although the precision was worse than that of TIMS it was adequate to discuss the origin of the Pb in these sea-waters. by ICP-MS. ICP-MS is well suited to the determination of U in river water. Palmer and Edmond (94/2234) conducted an extensive survey of U in rivers draining the Orinoco Amazon and Ganges basins using isotope dilution ICP-MS; the samples were exposed to UV radiation to break up dissolved organics and to help reduce build-up of an organic film on the ICP tubing and nebulizer. Controls on U concentrations in river waters and global fluxes of U are discussed.Smith (94/1283) used an enriched 201Hg spike for the determination of Hg in sediment and water samples by ID-ICP-MS. The low levels of Hg in natural waters required preconcentration onto gold traps and subsequent electrothermal heating and purging of the traps with argon directly into the ICP torch. The procedural LOD was 0.2 ng I-' from a 200ml sample and the accuracy was verified by measurement of the river water RM ORMS-1. Flow injection ID-ICP-MS has also been applied to the determination of Cu Cd and Pb in RMs SLRS-2 and CASS-2 River and Open Ocean Seawater respectively (94/2811). Because even ICP-MS cannot achieve the LODs required for some elements in environmental samples particularly waters many of the usual separation and preconcentration methods used for AAS in the past are now being applied to ICP-MS with all the attendant blank problems (see Table 2).An evaluation of ETV-ICP-MS for the rapid and accurate analysis of Arctic snow presents an alternative approach (94/2194). A 500-fold dilution of RM NASS-3 was used as a high-purity mixed matrix modifier without compromising the LODs. With the exception of Cd many of the heavy metals of interest could be determined in melted snow samples directly by ETV-ICP-MS. However larger concentration factors were achieved through evaporation in a clean environment; LODs in the fg range were reported. 2.2.5. Atomic fluorescence spectrometry and related techniques Cold vapour mercury determination is probably the most widely used vapour generation technique often in combination with atomic fluorescence spectrometry as an alternative to AAS.In recent years alkylating reagents have been used to generate volatile organo-metallic derivatives of other elements. Ultra- trace concentrations of Cd were successfully determined in drinking waters by AFS after alkylation with sodium tetra- ethylborate using a conventional continuous flow reactor (94/582). Interferences from transition metal ions were observed but were attenuated by the use of citrate as a masking agent. Cheam et al. (94/2931) claim to have published the first laser-excited atomic fluorescence spectrometric method for the direct determination of Pb at fg levels in sea-water. The practical LOD was 3 fg of Pb absolute or 1 ng 1-' which they believe to be the lowest absolute LOD reported for Pb in sea-water analysis.3. ANALYSIS OF SOILS PLANTS AND RELATED MATERIALS The 12 month period following the publication of last year's Update on environmental analysis (94/2403) has apparently resulted in little radical change in the methods being routinely employed for the analysis of soils plants and related materials. This is reflected in the contents of Table 3 which summarizes the methods published for these sample types over the review period. Section 3 therefore follows a similar format generally to that employed in recent years and highlights steady progress rather than major breakthroughs. 3.1. Soil and Plant Reference Materials All properly managed environmental analytical laboratories nowadays recognize the important role that certijied and 24R Journal of Analytical Atomic Spectrometry February 1995 Vol.10Table 3 SUMMARY OF ANALYSES OF SOILS PLANTS AND RELATED MATERIALS Technique; atomization; analyte form* AA;ETA;L Element Matrix Ag Orchard leaves Sample treatment/comments Reference 941227 9412966 Sample digested with 3 + 1 HN0,-H,O,; solution evaporated residue dissolved in 5 ml 1 mol 1-' HNO and diluted to 50 ml with 0.5% NH4SCN (as matrix modifier) solution; 1 p1 analysed in Mo tube atomizer Ag preconcentrated by complexation with NH4+ salt of dithiophosphoric acid 0,O-diethyl ester and adsorption onto carbon; Ag desorbed with small volume of HNO Mixture of Fe + La recommended for measurement of soluble A1 in soil Lyophilized and homogenized sample (200 pg) digested with 2.5 ml65% HNO + 50 pg V,O in microwave oven at 600 W for 90 s; digest cooled and diluted to 25 ml; detection limit was 0.02 pg 8-l digests; Se reduced with 6-8 moll-' HC1 and As with KI prior to determination; hydrides passed to heated quartz tube Samples pre-digested with HN03 + H,SO for 30 min then tubes were sealed and digestion continued for further 30 min; 3% NaBH in 1% NaOH used to generate hydrides of As and Se As and Se determined in HNO + H,SO + HClO As contents of Malaysian vegetables examined FI technique used to reduce AsV to As"'; 40 s time delay used to achieve complete reduction Au Pd and Pt preconcentrated by co-precipitation with Te Fire assay/AAS used for mineral soils INAA for humus in study of distribution and behaviour of Au near a Ni mine 70 "C 3 h and after almost complete evaporation leached with 0.5% HNO,; Cd and Pb determined Cd Cu and Zn extracted with 4 mol 1-' HNO at Soils digested with concentrated HNO at 160 "C for Atom trapping used to enhance sensitivity 270-fold Intracellular Cd sequestration studied Soil A A;ETA; L A1 As Soil Vegetable samples 9413 8 1 9411 29 AE;ICP;L AA; - Hy; L Vegetation soil sediments 941238 As As Biological samples AA; silica tube;L 941637 As As Vegetables Soil extracts AE;ICP Hy;L AA;- Hy;L AA;ETA;L AA;-;L 1NAA;-:S AA;-;L AA;ETA;L 9412099 9412891 Au Soils sediments Soils 941435 Au 941865 Cd Cd Sludge-treated soils Roadside soil 9411 32 941375 Cd Cd Taxodium ascendens Algae AA;-;L AA;-;L AE;ICP;L AA;-;L AA;ETA;L AA;F air-C,H,;L 941396 941456 Cd Bark leaves Study of distribution of Cd and Pb in roadside vegetation in Dhaka Effect of proximity of main road in Libya on Cd and Pb concentrations examined Sample digested with 20 + 3 + 1 + 1 HN0,-HC10,-HCl-HF; solution evaporated and residue dissolved in 0.25 mol 1-' HC1; Fe"' removed by extraction with 10 mmol 1-' hinokitiol in benzene; Co Cu and Ni extracted as APDC complexes into CHCl,; 40 pl aliquots of extract anal ysed RSD ranged from 4-8% using solid samples Co concentrated with 4-( 5-bromo-2-pyridy1azo)- 1,3-diaminobenzene and ammonium tetraphenylborate supported on microcrystalline naphthalene at pH 3.5-6; column content dissolved in DMF Correlations studied between Co Cu and Zn in vegetables and in the soils from which the vegetables came; no relationships found for Zn Particle size distribution of Cr-containing particles examined at contaminated sites Plants ashed in low-pressure 0 plasma; soils extracted with citric acid or subjected to acid digestion or alkali fusion; Na used as ionization buffer AA used to assess extraction of I3'Cs 89Sr and '*Cr with crown ethers from HNO extracts of soils; radiometric measurements also made See Co ref.94/65 See Cd ref. 94/132 Cu preconcentrated on oxine-loaded activated C Cu Fe and Mg complexes extracted with C,H,OH column; eluted in 4 mol 1-' HNO purified and separated by chromatography 9411734 Cd Roadside fruits and vegetables Pepperbush 9411 8 1 5 c o 94/65 c o c o Forage tea leaves corn meal Pepperbush pond sediment AA;F;L AA;ETA;S 9411 16 941 1693 co Soils vegetables AA;-;L 9411861 Cr c s Soil dust Plants soils soil extracts XRF;-;- AE;F air-C,H,;L 9412309 94/85 c s Soil AA;-;L 941385 c u c u cu Pepperbush Sludge-treated soils Pepper bush orchard leaves AA;F air-C,H,;L AA;-L AA;-;L 94/65 9411 32 941133 Chlorophyll and chlorophyllin complexes from vegetables AA;F;L c u 9411 90 Journal of Analytical Atomic Spectrometry February 1995 Vol.10 25 RTable 3 (continued) Technique; atomization; analyte form* AA;ETAS Sample treatment/comments Solid sampling gave recoveries of 94- 106% with a See Co ref. 94/1861 Sample pelletized with KI; emission at 350.5 nm from coefficient of variation of 6- 1 1 YO shock wave plasma measured; F content was 460-480 pg kg-' Problems of Fe loss during wet or dry ashing See Cu ref. 941190 highlighted; HN0,-HClO gave highest results Reference 9412.58 9411861 94/11 941168 941190 941 1 80 941252 9415 19 941720 941760 941388 941463 941946 9412299 94/85 941190 94/58 941331 9411 502 9411 542 9412849 9412850 94/65 941685 94/ 1 766 941284 941375 941591 94/1734 94/18 15 94/C 1894 Element Matrix c u Soil c u Soils vegetables F Green tea AA;-;L AE; laser; S Fe Plant and animal tissues AA;F air-C,H,;L AA;F;L Fe Chlorophyll and chlorophyllin complexes in vegetables Ge Ginseng AE; ICP Hy;L Sample digested with HN0,-HC10,-H2S0,; Ge preconcentrated by extraction from 9 mol 1-I HC1 solution into CCl,; back extracted into water amalgamation on Au gauze described.Detection limit was 2 ng 1-' in a flame-heated quartz cell Flow injection procedure for automated Samples wet digested prior to determination Cold vapour system coupled to ETA to enhance Problems reported in cold vapour FI Hg sensitivity determination from oxides of nitrogen which scavenge the reducing agent than gravimetric analysis as tetraphenyl potassium borate photometry for measurement of exchangeable K in soils Flame photometry was shown to yield lower results l'otentiometry compared favourably with flame Flame AAS shown to be simple and rapid 1. 1.11 portions of digest analysed in Mo microtube See Cs ref.94/85 See Cu ref. 94/190 atomizer; thiourea used as modifier Hg Environmental samples AA; quartz ce1l;L AA; cold vapour;L AA;ETA;L Hg Fruits vegetables Hg Plants grain AA;-;L Hg Sludges K Fertilizers AE;F;L AE;F;L K Soil extracts AA;F;L AA;ETAL K Fertilizers K Biological materials Li Plants soils soil extracts Mg Mo Soil Chlorophyll and chlorophyllin complexes in vegetables AE;F air-C,H,;L AA;F;L Mo from 10 pg soil extracted with 50 ml boiling H,O; 10 ml extract mixed with 2 ml acetate buffer and Mo extracted with 2 ml 3% 8-hydroxyquinoline in CHCl A novel flame photometric procedure Isotope discrimination studied for total- hydrolyzable-and non-hydrolyzable- ammonium- nitrate- amino- and mineralizable-N Two approaches using SIMS assessed for elucidation of nitrate absorption sites and pathway across roots Rapid system for "N determination described based on conversion to NO Continuous flow isotope ratio MS evaluated for monitoring labelled N and N,O emissions See Co ref.94/65 Samples digested with 2 + 1 HN0,-HC1 in a microwave oven; digest concentrated adjusted to pH 3 and diluted to 100ml; 1 ml 1 mol 1-' NaC104 added then 5 ml pH 3 glycene buffer; Ni extracted as 1,5-bis-(di-2-pyridyl-methylene) thio- carbonohydrazide into IBMK Concentrations of Ni and Zn in roadside vegetation and soil in Ghana studied; samples digested with HN03-HC104 Homogenized suspensions mineralized with HC1- HNO in a PTFE coil in a microwave oven using a FI system; samples of degassed digests introduced to furnace automatically See Cd ref.941315 l'b determined down to 2 ng ml-' in solution by plumbane generation using K2Cr,0 and lactic acid See Cd ref. 9411134 See Cd ref. 9411815 AA;ETA;L AE;F;L MS;-;- N as nitrate Vegetables 15N Soil components MS;-;S N as nitrate Corn root N as nitrate Plant and soil extracts MS;-;G MS;-;G AAF air-C,H,;L AA;ETA;L AEICP;L "N Ni Ni Ni Pb Pb Pb Pb Pb Pb 26 R Soil gaseous emissions Pepper bush Plant tissues Soil bark grass Olive leaves pine needles AA;ETA;L Roadside soil lichens sediments AA;ETA; L AE;ICP Hy;L AA;-;L AA;ETA;L XRF;-;- Bark leaves Roadside fruits and vegetables Soils Rapid microwave digestion used to clean up samples in field prior to XRF determination Journal of Analytical Atomic Spectrometry February 199.5 Vol I0Table 3 (continued) Element Pb Pd Pt Pt Pt Pt Rb REE REE REE Sb Se Se Se Se Sn Sn Sn Sn Te Ti T1 Zn Zn Zn Zn Various Various Various Various Various Various Matrix Soils vine leaves Soils sediments Soils sediments Plants Soils Beans tobacco Plants soils soil extracts Soil fertilizer Soils sediments Soils rocks sediments Sediments soils Vegetation soil sediments Biological samples Soil Plants geological materials River sediments River sediments Sediments Fungicides Environmental samples Shoots roots Cabbage leaf Sludge-treated soils Soil extracts Soil bark grass Soils vegetables Soils Food SRMs including wheat CRM soils and flours and corn flour Rice wheat tea Wheat shorts Leaves of black alder Technique; atomization; analyte form* AA;ETA;L AA;ETA;L AA;ETA;L AE;dc arc; L AE;ICP;L AA;ETA;L AE;F air-C,H,;L AE;ICP;L AA;ETA;L XRF;-;S AA;ETA;L AA;- Hy;L AA;- Hy; L AA;silica tube;L A&-;- AA;ETA;Sl PIXE;-;S AA;-;- A A; t u be;G AA;ETA;L AE;ICP;L ID;-;- AA;-;L AA;ETA;L AA;-;L AA;-;L XRF;-;S A A;ETA; L AA;F;L AA;ETA;L AE;ICP;L AE;ICP;S AA;-:L AE;ICP;L AE;ICP;L Sample treatment/comments Reference Samples subjected to microwave-assisted digestion with HNO or H202 for 15 min; this was more rapid than dry ashing procedure See Au ref. 941435 See Au ref.941435 Pt preconcentrated on silica gel Separon SGX C18 in presence of cationic surfactant and eluted with 96% C,H,OH; with Au as internal standard RSD was 6.3% Fire assay used for preconcentration in study of Pt and its behaviour in soils and sediments Samples digested with HN0,-HCl in PTFE bombs; Pt electrolytically deposited in pyrolytically-coated graphite tube; optimisation process described See Cs ref. 94/85 Effect of operational parameters studied; recoveries Optimization of conditions described for Ta foil-lined Automated analysis of samples pressed into discs Sample preparation systems compared for Sb were in range 90-110% with RSD <2.7% furnace described speciation including HNO3-H,SO4-HC1O4 HF-HN0,-H,SO,-HClO cold aqua regia and slurries in H,O or 4 mol 1-' HC1 See As ref.94/238 See As ref. 941637 PIXE shown to give similar results to AAS Samples digested with HN0,-HCl or HN03-H20,; digest diluted and adjusted to pH 2; Se absorbed by POLYORGS XXII; sorbent filtered and converted to slurry containing 0.5 mol I-' HCl; extract derivatized and analysed by GC-AAS tetraethyborate in aqueous buffer; volatile compounds purged trapped and then determined by AA Low recoveries of butyltin compounds observed for sediments with high chlorophyll hydrocarbon or sulfur contents tropolone in CH2CC12; extract evaporated and residue treated with sodium tetraethylborate; product injected into GC column; detection by AA using tube atomizer Te APDC complex extracted with 1 + 1 CHC1,-CCl from solution containing EDTA in acetate buffer at pH 6.2; Pd used as matrix modifier studied mol 1-' HC1 into toluene; p activity of '04Tl measured by scintillation counting Butyltin compounds extracted with CH,OH Alkyltins ethylated in situ with sodium Leached tributyltin fungicides extracted with Distribution of Ti in plants treated with Titavit T1 complex with Victoria Blue B extracted from 0.5 See Cd ref.941132 H3PO4 used as modifier to overcome interference See Ni ref. 9411766 See Co ref. 9411861 Portable XRF spectrometer used for screening soils Homogeneity of reference materials studied from C1- for hazardous metals Candidate CRMs digested with HNO under Solid samples mixed with graphite (2+ 3); Ba Co pressure and analysed for certification Cu Fe Pb and Zn determined; RSDs ranged from 5-14% Relationship between dietary fibre and inorganic Samples digested with HN03-HC10,; Al Cr Pb and elements studied Ti traced to emissions from aluminium plant Journal of Analytical Atomic Spectrometry February 1995 Vol.10 9412280 94/43 5 94/43 5 941755 941864 94f 1643 9418 5 9411236 94f 1790 94/2290 94/49 1 941238 941637 941902 94f1200 94/15 94/39 941786 9411094 9411 2 1 5 9411758 941245 941132 941369 9411766 941 186 1 9412 94/34 94/35 9411 15 941 1 66 941193 27 RTable 3 (continued) Element Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Matrix Tobacco leaves Soil KC1 extracts Coconut water Leaf litter sediments Roadside soils Mushroom species Biological samples Soils Particulates and water in forest Plants Filamentous bacteria Soils minerals Tree fine roots Soils Algae Moss Soils rocks Soil rocks Soils sediments Soils Leaves Soil extracts Vegetables treated with pesticides Soils rocks Soil sludge grass Leaves Algae plankton Tree rings Barley seedlings Soil extracts Wood ash Soils sediments Technique; atomization; analyte form* AA;ETA;S AE;ICP;L AA;F;L AA;F;L AE;ICP;L AA;-;L AA;ETA;L AE;ICP;L AA;- Hy;L MS;GD,S XRF-:- AE;ICP;L AA;ETA;Sl A A;ETA;L AA;-;L INAA;-;S 1NAA;- ;S AA;-;L AA;ETA;Sl MS;ICP laser; S XRF;-;S AA;F;L AE;F;L AE;arc; S AA;-;L XRF;-;S MS;laser;S XRF;-;S XRF;-;S XR F; - $3 XRF;-;L AA;-:L AE;ICP;L AA;-;L AA;ETA;L AE;ICP;L Sample treatment/comments S,lurry and direct solid sampling compared for Cd Co Ni and Pb; Pd used as modifier; agreement was reasonable Effects of KCl concentration and shaking time studied for Al Ca Mg and Mn; 0.5 mol 1-' KC1 for 10 min at a 1:15 soi1:solution ratio was reported to be optimal leaf analysis for some major nutrients Coconut water analysis compared favourably with Accumulation of Cd Cu Fe Mn and Ni studied Hg Ni Pb and Zn studied in roads near Zagreb Correlations between Sb uptake and uptakes of other Trace elements chelated on iminodiacetate-based metals studied resin and eluted into spectrometer with 3 mol 1-' HNO GD MS evaluated for soils and sediments F'articulates filtered and digested with 65% HNO,; trace elements in water concentrated by freeze drying Samples digested with HNO,+ 50% H202; vacuum monochromator used for P and S Adsorption of heavy metals by Thiothrix strain A1 studied by AAS For As Cd Cu Pb and V slurries gave similar results to solution samples Concentrations of Cd Cu Fe Mn Pb and Zn studied in 7 German forests Study suggests XRF allows more precise mapping of distribution of heavy metal contaminants Adsorption of trace metals by algae studied Concentrations of Cd Cu Ni Pb and Zn studied in Aspects of trace element soil geochemistry studied Aspects of trace element soil geochemistry studied Automated system for slurry introduction to furnace L.aser ablation used on pelletized samples for 30 Pleurozium schreberi over igneous rocks over metamorphic rocks described elements; calibration based upon INAA data for a standard soil sample; semiquantitative over the range 1-1000 pg g-' Monte Carlo simulation programme described and evaluated; agreement between predicted and observed spectra was good Pollution status of selected Indian soils studied using 4 mol 1-1 HNOJ or ammonium acetate extracts Samples digested with HN0,-H202; digest mixed with Pd and graphite powder evaporated and residue ground in agate mortar preconcentrated by solvent extraction and ion exchange; Sm used as internal standard J3etermination of 13 elements described with RSD better than 0.3 claimed Analysis of Nerium Oleander leaves used for pollution monitoring Organisms collected on polycarbonate filters and washed to remove sea-water; analysed by EDXRF Special platform built to allow automated analysis of tree rings Cr Cu Fe Mn and Zn determined following microwave-assisted acid digestion; EDXRF employed for analysis compared for extraction of Cu Fe Mn and Zn from soils Various techniques including TCP-AES used to study wood ash composition as a function of furnace temperature of 6 heavy metals (Cd Cu Fe Mn Pb Zn) presented Selected trace elements in HF-HNO digests Three chelating agents containing phosphonic groups Results for interlaboratory comparison for speciation Reference 941265 941380 941382 941381 9415 18 941532 941571 941606 941659 94/67 1 941784 941794 941837 941838 941894 941923 941925 941926 94/98 1 941996 94/1001 9411080 9411 104 941 1224 9411 383 9411563 9411574 9411 578 9411587 9411 664 9411 698 9411732 28R Journal of Analytical Atomic Spectrometry February 1995 VoE.10Table 3 (continued) Element Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Various Matrix Mosses Seaweed Soils sludge Green coffee Sound and wilt-diseased trees Mosses Zinc fertilizers Landfill soils Roadside soils Medicinal plants Pine needles citrus leaves Soils Leaves roots Soil extracts Aluminosilicate clays Plants sediments Leaves Biogeochemical reference Tea leaves Algae materials Technique; atomization; analyte form* AE1CP;L M S;ICP;L AA;-;L AA;-;L A E;I C P;G A A;ETA,L AA;F;L AE;ICP;L INAA;-;S AA;-;L AA;ETA;L INAA;-;S A A; ETA; L AA;-;L AA;ETA;L AA;F;L A A;ETA;SI AE;ICP;L MS;ICP;L XR F; - ;S M S;ICP;L AE;ICP;L MS;ICP;L MS;ICP;L AE;ICP;Sl AA;F air-C,H,;L Sample treatment/comments Techniques compared for the analysis of mosses as pollution indicators for 20 elements Eight mineralization procedures compared; Dry ashing at 450 O and treatment of ash with HCl + HF or wet digestion with HNO preferred Development of ETV system described Range of techniques evaluated for trace element ‘fingerprinting’ of coffee from diverse sources Radial distributions of elements in xylem compared Mosses studied as bioindicators of contamination with Cd Cu Pb and Zn Samples extracted with NH,Cl NH citrate or citric acid; materials high in extractable Cd Co or Pb should not be used as fertilizers Techniques compared for assessment of landfill leachates; separation with Chelex 100 used to improve selectivity in the ETAAS method converters assessed Contamination with Pt-group elements from catalytic Water extracts or HNO3-H2O digests analysed An echelle spectrometer with a photodiode array detector applied to multi-element continuum source AAS investigated for soils of urban public gardens; criteria defined to identify ‘unusual’ measurements Ultrasonic mixing and use of 5% HNO improved slurry stability; Cd Co Ni and Pb could be determined Ni and Pb Sampling and analytical variance thoroughly Two techniques gave similar results for Cd Cr Cu EDXRF applied to pelletized samples Applications of a particular ICP mass spectrometer Conditions compared for digestion for these two Characterization of reference materials following Novel system described for isolating appropriate finer Use of algae to concentrate trace metals from water described techniques microwave-assisted digestion described size fraction prior to slurry nebulization studied Reference 9411 745 9411 793 9411805 9411 8 55 9411857 9412 103 9412 127 9412 128 9412145 94/21 74 94/21 84 9412 5 5 5 9412580 9412643 9412695 9412852 9412853 94 128 54 94/29 14 9412967 * Hy indicates hydride and S L G and S1 signify solid liquid gaseous or slurry sample introduction respectively.Other abbreviations are listed elsewhere. standard reference materials play in analytical data quality control.Therefore any review of commercially available refer- ence materials is always welcome especially when it includes supplier addresses (94/979). Existing CRMs especially for complex and variable matrices like soils are used sometimes for quality assurance when attempting to provide certification for new RMs (94/35). Nevertheless homogeneity of agricultural RMs remains a cause for concern until good agreement is obtained for key elements in subsamples analysed by several different participating laboratories (94/34). One of the out- standing problems in the context of RMs is the provision of soil and sediment CRMs of acceptable homogeneity and stability for speciation studies (94/1732). 3.2. Sample Preparation able are much less common.Such studies are not attractive to funding agencies! An exception to the latter rule is the development of techniques for speciation which are still con- tinuing to attract attention from researchers and to evolve. Sampling strategy is a topic not considered that often by analytical atomic spectroscopists. However even those who rarely set foot outside the laboratory in the context of work occasionally run into data interpretation problems as a conse- quence of suspect results. Thompson and Maguire (94/2555) differentiated between sampling variance and analytical variance in the determination of Cd Cu Pb and Zn in soils from urban public gardens. Their robust statistical approach allowed defi- nition of criteria for identification of unusual measurements and for the assessment of analytical and sampling protocols.Developments in atomic spectrometry over recent years have dramatically lowered detection limits for many elements. Sample preparation remains the most time-consuming stage of most environmental analyses especially for soil and plant materials. It is no surprise therefore that the tide of minor improvements and variations continues to flow unabated. However in-depth systematic studies which are really valu- As a consequence greater care than ever is now needed to minimize contamination from whatever source. Razagui and Barlow (94/104) have recommended 5 min blending with a hot (80 “C) solution of 2% EDTA plus 2% citric acid as a wash procedure for minimization of contamination from blenders.Journal of Analytical Atomic Spectrometry February 1995 Vol. 10 29RFor meal samples significantly higher contamination with Cd Cr Cu Fe and Zn was noted from untreated blenders. 3.2.1. Sample dissolution There is little of interest to report about conventional acid digestion procedures apart from a claim by Beran (94/168) that Fe may be lost in the digestion of plant and animal tissues with HNO,. It was postulated that the losses were as insoluble silicates or phosphates and it was noted that higher yields were obtained if a HNO + HC104 mixture was used for sample digestion rather than 50% HN03. The trend over recent years towards use of microwave- assisted digestions has continued over the review period. It was claimed that oxidation of samples for wine production with H,O or HNO in a microwave digester reduced sample preparation time from 20 h to 30 min (94/2280).It has to be said however that the conventional procedure used for com- parison was a curiously complex one. Some claims made for reduction in sample preparation time are truly impressive. For example it has been claimed that As in 0.2 g sub-samples of homogenized and lyophilized vegetable samples may with microwave assistance be mineralized in 90 s with 2.5ml of 65% HNO and 50 pg Vz05 (94/129). The As was subsequently determined by HG-AAS. Reports are also still appearing in which conventional domestic microwave ovens are used for digestion (19/1614). In terms of precision and accuracy these can give reasonable results and it is good to see that safety is also being discussed.One of the most interesting reports published on sample preparation is on the automation of microwave-assisted digestion (94/284). An FI-based system was used with the homogenized biological samples in suspension form being oxidized prior to Pb determination by ETA using HC1+ HNO in a PTFE coil in a microwave oven. A gas diffusion cell was described which allowed degasification of the mineralized samples. 3.2.2. Novel extraction procedures Over recent years approaches to the extraction of soil alu- minium have attracted considerable attention especially in the context of acid deposition effects and A1 toxicity. One extract- ant quite often chosen often on a rather arbitrary basis is KCl. A study on the effect of KCl concentration shaking time and soil solution ratio is therefore particularly welcome for this element (94/380).Eventually a 10 min extraction with 0.5 mol 1-1 KCl at a soil solution ratio of 1 15 was recommended. The effects of changes in the same parameters on extraction of Ca Mg and Mn were also reported. In another study 2 mmol 1-' lanthanum solution was used to flocculate micro- particulate Al and 0.15 mmol I-' iron (111) was used to decomplex A1 bound to organic ligands prior to colorimetric A1 determination (94/38 1). If the lanthanum treatment only was used the results were the same as those obtained for total A1 determination in soil solutions by ICP-AES following filtration through 0.025 pm membrane filters. Acebal and colleagues (94/1664) have reported a comparison of the use of three phosphonic complexing agents on the extraction of Cu Fe Mn and Zn from soils prior to determi- nation of the elements by AAS.For such reagents to be used routinely a clear advantage to their use would need to be demonstrated for example superiority as indicators of bioavail- ability of trace elements. For soils which have been treated with heavy metal- contaminated sludges often quite mild acid extractants are suggested to be adequate for extraction of some loosely defined total pollutant heavy metal pool. In one study published this year 4 mol 1-1 HNO at 80 "C was used to assess Cd Cu and Zn distribution in soils (94/191). Care is needed in the interpret- ation of results of surveys based upon such procedures how- ever and also when applying the results prior to making land management decisions.For the determination of Cu Fe and Mg in chlorophyll and chlorophyllin complexes in vegetable samples ethanol has been used as an extractant (94/190). When the elements were subsequently determined by FAAS recoveries ranged from 64 to 88%. 3.2.3. Solvent extraction In spite of the fact that it is time consuming moderately expensive to use routinely and may require care to minimize hazards solvent extraction is still used in many laboratories around the world to enhance sensitivity especially if techniques with superior sensitivity such as ICP-MS are unavailable. Over the past 12 months procedures have been described for the determinations of Ge in ginseng (94/179) Ni in plant tissues (94/685) Te in diverse environmental samples (94/1215) Mo in soils (94/59) and Co Cu and Ni in pepperbush samples (94/65).Brief details of the procedures reagents and solvents used may be found under the appropriate elements and refer- ence numbers in Table 3. The last reference is interesting in that 40pl aliquots of a CHC1 extract were used for one drop-nebulization FAAS determination (94/65). Continuous nebulization of this solvent is not normally possible. 3.2.4. Other preconcentration procedures Even when ETAAS is used as a sensitive detection technique for some of the more exotic trace elements unusual preconcen- tration techniques must still be employed. For example copre- cipitation with tellurium has been found valuable for the concentration of Au Pd and Pt from a range of environmental samples including soils associated with geochemical pros- pecting (94/435).Copper from foliage samples has been concen- trated automatically by a dedicated FI system incorporating an oxine-loaded activated carbon column (94/133). The element was eluted with 4 mol 1-' HNO prior to determi- nation by AAS. 3.2.5. Speciation studies For several years now analysts have been employing hybrid techniques. Coupling atomic spectrometric detection to chrom- atographs for example has often been used for speciation of relatively volatile organometallic and similar compounds and early work in this field has been reviewed (94/1276). The review paid special attention to the problems associated with interfacing techniques. Several new reports of the use of such hybrid procedures have appeared especially for organotin compounds over recent months but the determinations are not without problems.A group of French workers has investigated the interference problems in the determination of butyltin in sediments with high sulfur and/or hydrocarbon concentrations (94/786). Recoveries may be low from such samples and from samples with high algae contents as a result of reduced efficiency of conversion to hydrides. As an alternative to HG it has been reported that butyltin compounds in sediments may be con- verted to ethyl derivatives by in-situ derivatization using sodium tetraethylborate (94/39). Purging and trapping are then used prior to GC separation. The sediment must be extracted with methanol containing 0.5 mol 1-1 HCl prior to derivatization of the alkyltin compounds present (94/15).Di- and tri-butyltin could be determined quantitatively in sediment by the ethylation technique whereas monobutyl tin gave low recoveries. However mono- and di-butyltin (but not tributyl- tin) could be determined by conversion to the hydrides prior to separation (94/15). Triphenyltin fungicides have also been determined following derivatization with sodium tetraethyl- borate (94/1094). It has also been suggested over the past year 30 R Journal of Analytical Atomic Spectrometry February 199.5 Vol. 10that supercritical fluid extraction should be useful for removal of organotin and organolead compounds from soils and sedi- ments after suitable complexation (94/C1964). The supercriti- cal COz used for extraction was modified with 5% methanol. Arsenic speciation in environmental samples has been attracting considerable attention over the past few years.Derivatization extraction and GC separation have been used to quantify lewisite and its breakdown products in soil (94/C1963). In this instance 1,3-propanedithiol was used for the derivatization. Chromium speciation studies invariably involve the separation of one or more inorganic species rather than the separation of organometallic compounds. An investigation of chronically contaminated sites in New Jersey revealed the presence of worryingly high concentrations of CrV' in some soil particle size fractions (94/2309). Wet chemical techniques were used to measure hexavalent and total chromium concentrations but XRF was used for multielement characterization of the particulates.3.2.6. Direct analysis of slurry samples While sample inhomogeneity limits the precision and use- fullness of direct analysis of weighed solid microsamples by atomic spectrometry reliable subsampling becomes much more feasible once a solid sample has been converted to a homogen- ized slurry. It is hardly surprising therefore that a number of researchers have used slurry atomization for ETA AS. Arsenic Cd Cu Pb and V have been successfully determined in 1% aqueous soil and mineral slurries by this technique although Se could not be measured because of loss during thermal pretreatment (94/794). After comparing slurries of cabbage leaves and roots in 0.05% HN03 0.05% HN03+0.04% Triton X-100 and 5% HNO Dobrowolski and Mierzwa (94/2580) concluded that the latter gave better slurry stability.They were able to determine Cd Co Ni and Pb by ETAAS and to obtain results comparable to those obtained following conventional wet ashing; however Pd was needed as a modifier for Cd determination. The same modifier was used for the determination of trace metals in tobacco leaves by both direct solid and slurry atomization (94/265). The two techniques gave similar results. If slurry atomization is to be used with an autosampler it is important to make sure that the slurry is homogenized prior to uptake of a subsample for analysis. Automated homogeniz- ation at the crucial stage is possible using an ultrasonic probe controlled by the autosampler (94/98 1 ). While most applications of slurry atomization in ETAAS involve analysis of homogenized sample slurries directly occasionally slurries are prepared from solid absorbants used for preconcentration.POLYORGS XXII has been used in this way for the determination of Se in geological and plant samples ( 94/1200). Few applications involving slurry nebulization into flames and plasmas have been reported. However an interesting study of the determination of concentrations of Al Ba Mg and Mn in tea leaf slurries by ICP-OES revealed that a particle size of < 80 pm is sufficient to allow accurate calibration with aqueous standards (94/2914). 3.3. Developments in Atomic Absorption Spectrometery Atomic absorption spectrometry is generally regarded as a single element technique although it has long been known that multielement analysis is possible with a continuum source and a suitable high resolution monochromator.A linear photo- diode array detector has been fitted to an echelle spectrometer for the determination of Cd Cr Cu Mn Mo and Pb by continuum source AAS (94/2 184). The system was successfully applied to the analysis of citrus leaves and pine needles. Evaluation of matrix modijiers for use in ETAAS continues to attract some attention although not to the same extent as in the recent past since suitable modifiers are available already for most determinations. Phosphoric acid has been rec- ommended for the determination of exchangeable Zn in soils after extraction of the element with 0.05 moll-' CaCl solution (941369). For the determination of Ag in biological samples by ETAAS using a Mo microtube atomizer NH4SCN has been suggested as a modifier (94/227).Although most environmental analysts tend to use platform atomization plus matrix modification in ETAAS for inter- ference-free analysis occasionally other approaches are still advocated. A tantalum foil-lined graphite furnace atomizer has been reported to be suitable for the determination of REE in soils and sediments (94/1790). Nowadays automated sample introduction to furnaces is regarded in most laboratories as an essential prerequisite to precise analysis by ETAAS. Other approaches are rare except for specific reasons. One of these reasons is if the determinant is to be preconcentrated inside the atomizer by electro- deposition. This approach has been applied to the determi- nation of Pt in tobacco beans and dust (94/1643). Cold vapour mercury determination is a well tried and tested technique capable of great selectivity and sensitivity.Innovation in this area is therefore not common. However two noteworthy papers have been published. Rokkjaer and colleagues (94/760) encountered interference problems from volatile nitrogen oxides formed by reactions with HN03 during sample decomposition. Pre-purging with argon over- came the problem. McIntosh (94/252) has described an auto- mated amalgamation technique for use in fully automated cold vapour Hg determinations. The system was tested successfully on a range of environmental samples. Those without access to adequate ETAAS apparatus occasionally resort to the use of atom trapping techniques to enhance sensitivity in FAAS.The slotted quartz tube cannot be applied to many elements but has been found useful for the determination of Cd in Taxodium ascendens (94/396). After atom trapping for 60 s the RSD was 4.1% for a 0.4 ng ml-' Cd solution. Finally although not strictly speaking atomic spectrometry mention should be made here of a useful review of the determination of halides by molecular absorption spectrometry using electrothermal graphite furnaces (94/1067). This tech- nique has been applied to various environmental samples including leaves. 3.4. Developments in Atomic Emission Spectrometry While flame-based AES is widely used routinely for a handful of elements the multielement analytical capability of most ICP-AES systems means that most notable developments relevant to this section are concerned with some aspect of the latter technique (94/552).In an assessment of mosses as bio- indicators of atmospheric pollution for example ICP-AES was sufficiently sensitive and selective to allow 20 elements to be determined (94/1745). The wide range of potential determi- nants sometimes allows routine measurement of species still not widely regarded as measurable by atomic spectrometry. For example P and S may be quantified directly if an argon- purged monochromator is used (94/971) so that indirect methods such as that suggested for sulfate may be unnecessary (94/1623). Indirect methods are more time consuming than direct methods but this may be acceptable if two determinants are measured together.Recently it has been reported that addition of a mixture of Ag and Ba allows simultaneous precipitation of C1- and SO2- which after dissolution allows the indirect determination of these two anions (94/1623). The low detection limits of ICP-AES for refractory oxide-forming Journal of Analytical Atomic Spectrometry February 1995 Vol. 10 31 Relements such as Ti is now allowing the distribution and function if any of such elements in plants to be studied (94/ 17 5 8). The limitation in ICP-AES imposed by the need for sample dissolution has again resulted in reports of AES techniques employing direct solid atomization. For F in biological samples such as powdered green tea the plasma induced by a TEA carbon dioxide laser has been used to excite emission at 350.5 nm (94/77). The F concentration was quite high at about 470 pg-' so the analysis is not particularly demanding with respect to sensitivity.A solid sampling system using a 2+3 sample +graphite mixture has been applied to the determi- nation of Ba Co Cu Fe Pb and Zn in flour and tea leaf samples by ICP-AES (94/115). If sensitivity enhancement proves necessary in ICP-AES several approaches are possible. Small sample vaporization from graphite cups improves sensitivity and allows the direct analysis of some solid environmental samples (94/1805). Alternatively for elements such as Pb HG techniques may be exploited to measure low concentrations of the element in sediments and lichens (94/597). In this instance a potassium dichromate +lactic acid digestion was used for sample oxidation. 3.5.Developments in Mass Spectrometry Inductively coupled plasma mass spectrometry is sometimes reported to be well suited to the analysis of soil extracts (94/2643). For total element analysis however the high concen- trations of major elements in the sample and in dissolution reagents may impose serious constraints for a number of reasons. It has been shown that high calcium concentrations may influence instrumental stability for example (94/641). It is possible that direct analysis of solids for example by laser ablation ICP-MS may eradicate some of these problems. This technique has been applied to the determination of 30 elements in small pellets of 7 Chinese reference soils (94/996). The results obtained compared favourably with those obtained by INAA for a number of elements but reliable quantification was not possible for elements present at concentrations < 1 pg g-'.Another approach is to apply GDMS to soil analysis (94/606). This allowed estimation of the concentrations of up to 51 elements although the accuracy and precision were not particularly encouraging. The determination of I5N by MS continues to attract atten- tion because of the value of this tracer in studies of N cycling in the soil-plant-water system (94/1502). Two useful papers have been published on the automation of this determination one concerned with measurement of nitrate-"N in plant and soil extracts (94/2849) and the other with measurement of labelled N and N20 (94/2850). The latter procedure allowed six samples to be processed automatically per hour.One of the major limitations to the application of state-of- the-art atomic spectrometry in environmental analysis is the need to bring together solutions and problems or people who comprehend both. Thus reports of studies such as that using secondary ion mass spectrometry to study nitrate absorption sites and the radial transport pathway across corn roots are particularly encouraging (94/1542). Two approaches were evaluated. The first involved imaging of C1- peaks using 0- bombardment of quench-frozen freeze-substituted low tem- perature-embedded cross sections of roots 0.5 pm thick. The second involved imaging the l2CI5N peak using Cs' bombard- ment. Other workers have also discussed the potential of various tracer ions as probes for imaging ion transport in biological systems (94/1543).3.6. Developments in X-ray Spectrometry Over the past few years there have been reports at regular intervals of the merits of X-ray fluorescence for soil mapping. The technique may be used in the field to allow a higher resolution sampling pattern and more precise location of anomalies and heavy metal contamination zones at polluted sites (94/2 94/838). For tree ring analysis EDXRF has been used for a number of years. Selin et al. (94/1578) have described an automated sample positioning table dedicated to this analysis which allows the sample to be moved under computer control in 5 pm incremental steps in any of three directions. Detection limits were in the pg g-' range for medium-to-heavy elements.Proton-induced X-ray emission (PIXE) is not widely used in soil or plant analysis. However it has been suggested for the determination of Se in soils an otherwise problematic determi- nation (94/902). The authors concluded that PIXE was fast and non-destructive and gave results similar to those obtained by conventional AAS. 3.7. Nuclear Techniques Environmental analysts in many laboratories for various reasons tend to ignore nuclear and nuclear-related techniques for the analysis of soils plants and related materials. For those that are considering their use a review of their applicability to dust soils and sediments by Sansoni (94/2816) might serve as a useful introduction. 4. ANALYSIS OF GEOLOGICAL MATERIALS 4.1. Introduction In contrast to the previous review period (94/2403) which was dominated by applications using ICP-MS there is no particu- lar aspect of the analysis of geological materials over the past year which merits special mention.Rather it has been a period of consolidation of existing techniques. However some notice- able trends in analysis can be discerned and it will prove interesting to see if these continue in the future. The need to obtain reliable data from ever smaller samples has led to many applications using LA and the need for lower LOD values has resulted in increased use of preconcentration methods. It is always useful to have an overview of analytical tech- niques and several wide-ranging reviews have been published. Potts et al. (94/2374) considered the contribution advances in analytical technology have made to modern inorganic geo- chemistry citing 123 refs.Sen Gupta (94/2387) reviewed 25 years of research and application of ETAAS and FAAS to geochemistry. Sansoni (94/28 16) reviewed the application of NAA thermal NAA ICP-MS XRF and TXRF among other techniques in environmental research and monitoring in a paper containing 18 refs. 4.2. Sample Preparation 4.2.1. Solid sample introduction The quantitative determination of major trace and REEs in geological samples by laser ablation coupled to inductively coupled plasma mass spectrometry has been approached from two different standpoints. Jarvis and Williams (94/1364) ana- lysed pressed powder pellets of seven RMs and achieved results which were generally accurate to within 10% of the certified value.The LOD for most elements was <0.1 pg g-'. They found that the chemical and mineralogical composition of samples influenced the ablation behaviour. This technique offers the possibility of very rapid analysis. Fedorowich et al. (94/1363) preferred to produce glass beads by melting small amounts of rock powder on a tungsten heating strip under Ar at 275 kPa to suppress the loss of volatile elements such as B K Li and Na. The system was tested on six RMs. Most results fell within 5% of the stated values. The LOD values ranged from 0.02 to 0.3 pg g-'. They found that the ablation efficiency 32 R Journal of Analytical Atomic Spectrometry February 199.5 V01.10using a Nd YAG laser could be affected by the REE and Fe" contents of samples.Several investigations using a laser ablation microprobe system with measurements by ICP-MS have been reported. Chenery and Cook (94/292) were able to determine REEs in single grains of clinopyroxene and monazite at the ng 8-l level. Aqueous standards were used for calibration. The LOD values obtained were superior to those by EPMA but the latter technique was more precise. Feng et al. (94/1387) deter- mined 207Pb:206Pb ratios on a single grain of zircon which enabled the mineral to be dated. A comparison with results obtained from TIMS using conventional U-Pb dating showed agreement to 1%. A similar technique enabled the age of single grains of pitchblende and zircon to be determined by measuring U Pb isotopic ratios (94/2227). Analysis of the coatings on pebbles obtained from stream sediments by LA-ICP-AES provided a useful indication of mineralization in the surrounding areas.A survey around a gold mining area in Wales revealed the presence of anomalous concentrations of As Cd Co Cu Mo Pb and Zn in the coatings (94/940). A method using LA-ICP-MS was able to detect Au at the ng 8-l level in rocks after ablating a 50pg sample (94/1424). In-situ trace element determination in minerals by LA-MP- ICP-MS was investigated by Jackson et al. (94/1357). Calibration using a spiked NIST Silicate Glass SRM provided good accuracy precision (< 10% at the 60 pg 8-l level) and an LOD of about 0.5 pg g-'. Methods of analysis using slurry nebulization are not so evident this year compared with the last review period. A noteworthy exception is a paper by Halicz et al.(94/570) who described a preparation scheme for the quantitative analysis of geological materials. They used a 3-dimensional turbulent mixer mill to produce dimensions of < 1.5 pm for 95% of particles. A V-groove Ebdon nebulizer and a Trassy-Mermet torch system enabled major minor and trace elements to be determined by ICP-AES. Calibration used aqueous standards and k-factors were applied to compensate for incomplete recoveries. Analysis of results obtained from 24 RMs showed that particle size is the constraining factor in the quantitative analysis of geological samples. Spanish workers (94/2956) determined Pb in sediments by ETAAS using slurry introduc- tion. The use of Pd + Mg(N03)2 as a modifier was optimized two charring steps being required.The precision of the method was less than 5% with an LOD of 0.22 pg I-' Pb. The method was tested on a Canadian sediment RM. 4.2.2. Decomposition with acids Techniques of sample decomposition with the usual mixtures of acids (HC1 HNO HClO and HF) are well established and there is little of note to report on that front. The use of sample digestion with microwave heating in a sealed container is a method which is becoming more frequently used. Paukert (94/370) decomposed 500 mg of geological samples treated with 20ml HCl by heating the mixture in a microwave oven for 1 h. Any undissolved residue was fused with Na2C0 + Na2B,07. The determination of REEs by ICP-AES demonstrated that the procedure was about 98% efficient. Gluodenis and Tyson (94/578) employed a stopped-flow micro- wave system for the decomposition of slurries.Slurry samples were mixed with HNO and then heated at a pressure of 400 lb in-' for 5 min This method was tested on a coal RM and low recoveries suggested an incomplete dissolution of sili- cate constituents which is hardly surprising! Conventional heating systems are often used for sample decomposition in a sealed system. Yin et al. (94/2235) heated molybdenite overnight at 90 "C with 6 mol 1-l H2S04 + CrO in a sealed Savillex container after irradiation with thermal neutrons. Negative TIMS was used to measure 1860s. .1920s and lg8Os 1920s ratios after separation of 0 s by distillation. This procedure avoids problems of sample inhomogeneity and isotopic exchange difficulties when using an 0 s spike.Russian workers (94/1200) used a mixture of HCl+HN03 or HN03 + H,02 to decompose geological materials by heating the mixture to 200°C in an autoclave prior to determining Se by ETAAS. Staudt et al. (94/2226) used a selective decomposition method to remove non-dolomitic phases such as calcite halite and gypsum when determining trace elements in dolomite. Treatment of samples with 4% CH,COOH followed by H,O produced a dolomite of greater than 99% purity. After solution in 3% HNO the Na content was determined using a DCP. 4.2.3. Decomposition using fusion The most common method used for fusion of geological materials is decomposition with alkalinefluxes. Many variations of conditions and reagents have been tried in order to create suitable fluxing conditions.Fusion of non-ferrous metallic ores with 84% Li2B407+ 14% Li2C0,+2% LiNO at 800°C for 30min produced a glass bead suitable for analysis by XRF (94/1157). Determinations of Cu Mo Pb W and Zn using synthetic standards gave results comparable with those obtained by ICP-AES and FAAS. The extra solids introduced by a flux can be a problem in analysis by ICP-MS. Rivoldini and Fadda (94/2962) overcame this difficulty by fusing rock samples with either K,CO or K2B407 and then removing potassium by precipitation as KCIO and boron by evapor- ation as BF3. The procedure was tested for the determination of 14 REEs Sc and Y by using 9 RMs. Fusion with K2C03 was found to give the most precise results but K2B407 fusion was preferred for the analysis of large batches of samples.4.2.4. Separation and preconcentration 4.2.4.1 Solvent extraction. Two different extraction systems for the determination of T1 have been reported. In the first method Guo et al. (94/636) decomposed rocks using an HF+HN03 attack. Iron meteorite material was digested by refluxing with HNO,. The residue remaining after evaporation of these solutions to dryness was heated with 10ml of 3 mol 1-l H2S04 followed by dilution to 50 or 100ml. A 2-4ml portion of the dilute H2S04 solution was mixed with KI+K,HPO and the iodo-complex of TI extracted into IBMK. Washing the extract with 3 mol 1-1 H2S04 removed residual Fe and determination by ETAAS gave an LOD for the method of 2 ng g-' T1 in a sample. The second method used the ion-association complex formed between T1 and Victoria Blue B which was extracted into toluene from a 0.5 mol 1-1 HCl solution.Using an ID technique for analysis enabled amounts as low as 0.2 pg TI in rocks to be measured (94/245). The extraction of gold from geochemical samples was achieved with 0.2% Br + 1% NH,C1 as the extractant after preconcentration of Au on polyurethane foam. Determination by ETAAS gave an LOD of 0.06 ng 8-l Au (94/208). Another extractant used for the determination of Au was 3-methylbutan-2-01 (94/2805). The determination of toxic elements at trace levels has been facilitated by solvent extraction methods. Cadmium in lime- stones was extracted with APDC and IBMK and determined by FAAS (94/1726). Lead in phosphates was extracted with diphenylthiocarbazide + CC14 after an alkaline fusion of the sample.Again determination was by FAAS (94/1258). The extraction and quantification of alkylmercury compounds in sediments was the subject of a conference presentation (94/C 1965). After sample acidification the organomercurial Journal of Analytical Atomic Spectrometry February 1995 Vol. 10 33Rcompounds were extracted into toluene separated using gel permeation chromatography and determined by AES. 4.2.4.2. Ion exchange. Brenner et al. (94/1078) reported a cation-exchange technique for separating REEs from matrix elements. Unwanted elements were eluted with a 3 + 1 mixture of 3 mol 1-' HN03+2 mol 1-l HCl followed by elution of REEs with 7 mol 1-' HN03. An ultrasonic nebulization sample introduction system was used for determination of REEs by ICP-AES with LOD values ranging from 0.06 to 9.4 pg 1-l of REE. Trace amounts of Ag Ru and Te in uraninite were determined by TIMS after a cation-exchange separation (94/2223).Silver and Te were eluted with 9 mol 1-' HCl and 0.5 moll-' HCl respectively; Ru was separated by distillation and then purified on a cation exchange resin to remove Ca and Sr. An anion exchange separation of Au after acid decomposition of ores enabled interfering Hg and Zn to be removed (94/1092). Analysis of the dried homogenized resin by XRF using the Au La line gave results agreeing with values obtained by NAA. The determination of 99Tc requires a separation from Ru. Anion exchange was among several methods examined (94/2792). 4.2.4.3. Coprecipitation. Coprecipitation is widely used as a separation and preconcentration method in spite of the need to filter or centrifuge the precipitate produced.Coprecipitation with tellurium followed by ETAAS was used for the determi- nation of Au Pd and Pt in sediments from Canadian lakes. The LOD of this method was 0.05 ng g-' for Au and Pd and 2 ng g-' for Pt (94/435). Niobium and tantalum are difficult elements to determine in geological materials because of their low abundance coupled with the ease with which they tend to precipitate from solutions. Kubova et al. (94/2389) used tartaric acid to stabilize the solution obtained after sample decomposition. Precipitation of these elements with cupferron was followed by analysis of the dissolved precipitate by ICP-AES. The determination of silver in ores was reported using two different coprecipitation schemes.The first employed precipi- tation with hydrazine hydrate using Au as a carrier (94/1152). The second used CuS as a precipitating agent in the presence of thiourea and the trisodium salt of EDTA at pH 8.5-9.3. The precipitate was ashed at 450°C redissolved in HC1+HNO3 and the Ag content determined by FAAS (94/2806). A continuous precipitation dissolution system mentioned in last year's review as a conference presentation has appeared in a recent publication (94/2982). The determination of trace amounts of Ni in rocks used continuous precipitation of Ni with 1 -nitroso-2-naphthol redissolution of the precipitate in ethanol and measurement by FAAS. About 15 samples h-l could be analysed and the system was tested on six RMs.4.2.4.4. Vapour generation. The need for reliable determi- nation of organotin compounds because of their toxicity has resulted in two interesting papers being published in the past year. Quevauviller et al. (94/786) used HG coupled with GC-AAS to determine mono- di- and tri-butyltin in sediments. They found samples containing high levels of S and hydro- carbons gave poor recoveries of organotins probably due to inhibition of the HG process. This difficulty was avoided by Cai et al. (94/39) who employed in situ ethylation of organotins using sodium tetraethylborate. The Sn-C,H bond formed was more thermally stable than the Sn-H bond. Measurement again used a GC-AAS system and the LODs of this method were 9 38 and 12 ng g-' Sn for mono- di- and tri-butyltin respectively. Mercury is another toxic element and the determination of methylmercury (MeHg) compounds is important for pollution studies.Horvat et al. (94/1615) isolated MeHg from sediments by distillation followed by ethylation and determination of Hg with GC-CV-AF. This technique was compared with alkaline digestion and HC1 leaching methods. The distillation method avoided matrix effects during the ethylation stage and provided more accurate results. The technique was tested on two sediment RMs; the LOD was as low as 1 pg 1-l MeHg using a 100 mg sample. The determination of Se in samples is facilitated by HG. Measurement by ICP-MS is sometimes beset by signal instabil- ity and interferences due to the presence of chloride. These were overcome by the use of a tubular membrane gas-liquid separator instead of the usual U-tube (94/2750).The use of a vesicular medium for a continuous flow HG system to determine As in sediments was claimed to provide several advantages over a conventional HG system (94/325). Arsine was generated from a didodecyldimethylammonium bromide vesicular medium and the system was said to produce improved HG improved precision and a greater tolerance to interferences. The method had an LOD of 0.6 ng g-' As and was tested on two sedimentary RMs. 4.2.4.5. Other separation methods. Various forms of chroma- tographic separation often in conjunction with determination of REEs by ICP-AES have been described during the past year. Pukhovskaya et al. (94/1182) used countercurrent chrom- atography (CCC) for the group separation of REEs in rocks.This technique is more rapid than usual separation methods such as ion exchange and needs only a one-stage separation step. It is possible that methods could be devised to separate other trace elements from matrix elements by CCC. Russian workers tested three methods for the preconcentration of REEs (94/2279) precipitation of REE hydroxides; TLC separation with circular elution using 0.1 mol 1- oxalic acid + 2 mol 1-l NH,Cl; and LC using HCl as the mobile phase. They found LC produced the best results. An unusual method for the separation of trace elements involves preconcentration with immobilized algae. Elmahadi and Greenway (94/2967) compared the properties of two algae for the preconcentration of Ag Cr"' CrV' and Cu.They found that maximum recovery of these elements depended on pH values. Determination by FAAS gave LOD values of 2.0 20 40 and 0.05 ng ml-I for Ag Cr"' CrV1 and Cu respectively. The method was tested on RM MESS-1 for Cu and Zn. 4.3. Instrumental Analysis 4.3.1. Atomic absorption spectrometry The number of papers reporting developments in AAS tech- niques has remained at a similar level to last year. Several have described JEow injection methods often combined with a separation technique as a means of improving the overall LOD. Lin and Hwang (94/1650) determined Au and Cu in ores by FAAS using an on-line FI system coupled to a gravitational phase separator. An LOD of 1.8 pg 1-l Au and 1.0 pg I-' Cu was obtained. Chinese workers (94/11) described an FI on-line fibre column separation and preconcentration system for the determination of Au in ores which gave an LOD of 0.2 1-18 ml-' Au with an RSD of 2.2% at 80 pg ml-I Au.A further application of FI determined Hg in zinc ores (94/2592). After an acid digestion and the addition of K2Cr207 reduction with SnCl liberated Hg atoms which were detected at 253.7 nm. The LOD of this method was 80 ng g-'. A technique worthy of note is simultaneous multi-element atomic absorption. This was used by Farah and Sneddon (94/778) to determine Cu Fe Mn and Zn in sediments. It was necessary to use Smith-Hieftje background correction to obtain the best results. 34R Journal of Analytical Atomic Spectrometry February 1995 Vol. 10An economical method for the determination of Au in geological materials was described by Tewari and Gupta (94/2349).The extraction of Au from 10 g samples involved heating with a mixture of HC1 and calcium chloro- hypochlorite. After coprecipitation with Hg centrifugation and subsequent dissolution of the precipitate in HC1+ HN03 Au was determined by FAAS with an LOD of 0.05 pg 8-l. This method was claimed to be more accurate and rapid than decomposition using HC1+ HN03. Electrothermal atomization methods have been widely reported during the last year as can be seen in Table4. The determination of Au in ores using a graphite tube conditioned with polyacrylamidine thiocyanate (94/395) enabled Au to be electrostatically preconcentrated on the tube thus eliminating interferences from Ag Ir Pd Pt and Rh.Sen Gupta (94/1648) described a method to determine Ag Au Ir Pd Pt Rh and Ru in silicate rocks. An acid decomposition was followed by preconcentration using ion exchange and measurement of the determinands with simultaneous multi-element ETAAS equipped with a Zeeman background corrector. The method was tested on three Canadian RMs. Trace elements determined using ETAAS include In and T1 in geological samples (94/ 1151); Cd Cu Ni and Pb in sediments (94/2642); Sr in sediments using ammonium EDTA as a matrix modifier (94/1154); and Ni in ores using NH4V03 to increase sensi- tivity (94/206). Paukert and Rubeska (94/986) studied the effects of fusion charge composition on the determination of PGEs using a NiS button for collection. Two parameters the extraction ratio and %S in the collector were defined.It was found that recoveries of PGEs determined by ETAAS depended on the values of these parameters. For full recovery the extraction ratio should be greater than 30 and the %S in the collector should be between 30-50%. The precision and accuracy of the procedure were tested on three Canadian RMs. 4.3.2. AtomicJluorescence spectrometry A technique which is seldom reported but still has devotees is atomic fluorescence spectrometry. Hydride generation separ- ation methods followed by measurement using AFS have been applied to the determination of several trace elements in geological samples Bi (94/153); Ge (94/1097); and As Bi and Se (94/2710). A conference presentation by Tyson and Yehl (94/C1932) examined the possibility of using FI methods in conjunction with AFS for the determination of Au Cr"' and CrV1. 4.3.3.Atomic emission spectrometry Any system which improves the LOD obtainable using ICP- AES is very welcome to analysts. Brenner and Dorfman (94/599) described the performance of an ultrasonic nebulizer (USN) for the determination of REEs in phosphates and sedimentary rocks. They demonstrated that the LOD using a USN-ICP-AES system was very similar to that obtainable by ICP-MS. A study of five different decomposition routines showed that it was essential to use a total decomposition method to obtain results which compared well with literature values. 4.3.4. Inductively coupled plasma mass spectrometry After the large number of investigations using ICP-MS tech- niques reported last year it was perhaps to be expected that the number of applications this year would show a decrease.However interest in the determination of platinum group elements and gold is always considerable. Inhomogeneous distribution of Au and the PGEs in rocks was minimized by Perry et al. (94/2386) who extracted the precious metals from a 250g sample by means of dry chlorination in a specially designed tube. Dissolution of the analytes with 10% HCl was followed by determination using ICP-MS blank values being <0.1 ng 8-l for most elements. Sun et al. (94/1177) used a screw-capped Savillex jar to dissolve the NiS button which preconcentrated the precious metals. By this method it was possible to avoid common disadvantages of the NiS technique i.e. powdering of the button could produce losses of NiS and open beaker dissolution could increase blank values and loss of volatile components.The Te precipitate used for subsequent coprecipitation of the precious metals was collected by centrifu- gation thus ensuring a full recovery. Determination by ICP-MS showed recoveries close to 100% (Au 90%; Os 65%) with RSD values of <5% for Au Ir Pd Rh and Ru 9% for Pt and <30% for 0 s and Re. The versatility and sensitivity of ICP-MS was amply demon- strated by two studies on reference materials. German workers (94/1382) determined 37 trace elements in 28 RMs both after a mixed acid attack in a pressure vessel and after a lithium borate fusion. Although agreement with certified values was generally good lower results were obtained for REE and Y.In the second study Poitrasson et al. (94/2229) determined low levels of Nb and Ta in silicates reporting LOD values of 40 ng g-' Nb and 0.8 ng g-' Ta. Internal standards used were "Mo for Nb and 18'Re for Ta. When a sample of 100mg was analysed certain RMs exhibited a degree of Nb-Ta heterogen- eity which was not evident in a 1 g sample. Isobaric interferences and memory eflects are two difficulties which beset trace element determination by ICP-MS. A study into the former by Longerich (94/564) investigated the effect of using HCl or HC104 solutions when determining the REEs. He found a solution containing HC104 produced enhanced levels of oxychlorine polyatomic ions compared with an HCl solution. These ions could then react with Ca or Mg present in the sample to produce isobaric interferences e.g.40Ca37C1'604+ interferes with 14'Pr+ . These reactions were not exhibited by Al Fe K Mn Na Sc or Ti. Memory effects can cause serious problems in the determination of ultra-trace elements. Chinese workers (94/2865) overcame such effects in the determination of 0s-Re isotopes in molybdenite by rinsing the entire system with an oxidizing agent. 4.3.5. Other mass spectrometric methods Accelerator mass spectrometry was used by Rucklidge et al. (94/1356) to determine all the PGEs Ag and Au in sulfide concentrates and the very low LOD values obtained on microgram quantities of material demonstrated the great sensi- tivity of this technique. A similar approach by Chai et al. (94/1359) when studying a Chinese ore deposit demonstrated that the sulfide phases were enriched in Os Pd Rh and Ru and depleted in Au Ir and Pt.An interesting investigation on extraterrestrial matter by Kutschera et al. (94/1442) detected the presence of 59Ni formed from interaction with cosmic rays. Separation of 59Ni28+ from 59C027+ was achieved using a magnetic spectrograph. An almost identical procedure adopted by Australian workers obtained a sensitivity limit of 5 x for a 59Ni Ni ratio (94/2734). Resonance ion mass spectrometry was used in conjunction with thermal atomization methods to determine Rh and Ru in ancient geological deposits and rock samples (94/1797). An alternative sample introduction method is to use a laser system and a two-step laser excitation technique was employed by Bulgarian workers (94/2191) to determine trace amounts of Lu as low as 0.1 pg 8-l in geological samples.Results obtained compared favourably with NAA values. Continuous wave lasers were used to excite samples prior to determining 230Th 232Th ratios by RIMS (94/2830) and the ionization efficiency precision accuracy and bias with respect to both broad-band and narrow-band lasers were discussed. Journal of Analytical Atomic Spectrometry February 1995 Vol. 10 35 RTable 4 SUMMARY OF ANALYSES OF GEOLOGICAL MATERIALS Technique; atomization; analyte form* XRF;-;S A A;ETA; S MS;ETA;L Sample treatmentlcomments Determinand precipitated from solution filtered and Solid sample analysed directly from graphite platform. Thermal ionization sample introduction used to analysed as a thin film (79 ng g-'! determine isotopic compositions after determinands were separated from the sample matrix by ion- exchange chromatography Sample digested in HC1+ HF + HN03 + HClO,.Ag complexed with 15 mmol 1-' N-phenylthiobenzamide in butyl acetate; organic phase directly aspirated Ag preconcentrated from aqua regia digestate by precipitation on a CuS collector in the presence of Na,EDTA thiourea and pH 8.5-9.3 buffer. Collector filtered ashed and dissolved in aqua regia Two covalently immobilized algae compared for the preconcentration of Ag' Cu2+ Cr3+ and Cr6+ Sample sintered with NazO2 and dissolved in H20 Sample digested in HC1+HN03 taken to dryness Si removed by evaporation with HF and H2S0 residue filtered off and fused with Na2C03 and cooled melt dissolved in filtrate didodecyldimethylammonium bromide vesicular medium which improved detection limits by a factor of 2 (0.6 pg ml-') Continuous flow hydride generator design described.Se Te and Hg also tested on the system Background correction method for the simultaneous determination of the determinands by EDXRF described Samples extracted with aqua regia and reduced with thiourea and ascorbic acid Detection limit for As Bi and Sb 0.01 pg ml-' and 0.001 pg ml-I for Hg Samples digested in aqua regia; sample solution diluted and 5% thiourea + 5% ascorbic acid added prior to measurement (0.79 ng ml-' As 0.46 ng ml-' Bi and 0.29 ng ml-' Sb) FI sample introduction used with an on-line 8531 fibre used to preconcentrate Au prior to elution into the flame (0.2 pg ml-') Au preconcentrated on polyurethane foam; after ashing Au extracted with 0.2% Br2+ 1% NH,Cl with a recovery of 96-100% (0.06 pg kg-') Sequential acid dissolution used to determine the different chemical forms of Au in the ore material Graphite atomizer tube coated with a thin film of polyacrylamidine thiocyanate and then soaked in the Au sample solution prior to atomization. Sensitivity of 3.5 x lo-'' mol 1-' for 1% absorption Te coprecipitation used to preconcentrate determinant.Results used to study Au Pd and Pt transport and fixation from a mineralized occurrence (0.5 pg kg-' for Au and Pd 2.0 pg kg-' for Pt) filtered. Filtrate applied to column of macroporous X-5 adsorption resin impregnated with (2-ethylhexy1)phosphine oxide. Au eluted with 0.2 mol I-' thiourea+ 1 mol I-' HC1+0.5 mol 1-' acetic acid Determinand concentrated from different size fractions by fire assay Sample digested in aqua regia taken to dryness and redissolved in 6 mol I-' HC1.Au collected on Dowex 2-X10 anion-exchange column washed dried and used as solid sample. Results agreed with values obtained by NAA Sample digested in KC10 + HNO + HC1. Cooled mixture diluted H202 and polyurethane foam added and shaken for 30 min. Au extracted from washed foam with thiourea + HCl SIMS and LIMS used to map Au distribution in the mineral Arsine generated from by NaBH reduction in a Sample boiled in aqua regia + 0.2% animal glue and RLference 94/1152 9411 2 13 9412223 94/27 15 9412806 9412967 9411764 9412604 941525 Element Matrix Ag Ores Ag Rock and minerals 4 3 Uraninite Ag Ores Ag Sulfide ore AA;F;L AA;F air-C,H2;L A!? Estuarine sediment A1 Chromitites A1 Iron ore AA;F;L U ; F C2Hz-NzO;L As Sediments AE;ICP,Hy;- As As Geological samples 94/126 1 9411 590 Marine sediment RM Chemical exploration samples Sediments AF;-;L AE;ICP,Hy;- AF;Hy;L 9411782 9411787 9412710 As As As Geochemical samples Au Ores AA;F;L 94/11 Geochemical samples AA;ETAL 941208 Au AA;F;L AA;ETA;L 941384 941395 Au Au Ores Ores AU Soils and sediments A A;ETA,L 941435 Au Ores AA;F;L 941645 Point bar and pavement Ore sediments AA;F;L XRF;-;S 941866 9411092 Au Au Geologcal samples AA;F;L AA;ETA; L 9411 237 Au MS;-;S Au Arsenian pyrite 9411358 36 R Journal of Analytical Atomic Spectrometry February 1995 Vol.10Table 4 (continued) Technique; atomization; analyte form* MS;ICP;S Element Matrix Au Rocks Sample treatment/comments Reference 9411424 9411535 9411650 Nd:YAG laser microprobe sample introduction used Semiquantitative imaging of submicroscopic Au in On-line FI liquid-liquid extraction system with (1 ng &-'I mineral grains described gravitational phase separator described.Enhancement factor of 70 and 78 obtained for Au and Cu respectively (1.8 and 1.0 pg 1-' respectively) Samples heated with a mixture of HCl +bleaching powder followed by co-precipitation of Au with Hg; precipitate dissolved in aqua regia (0.05 pg g-'1 Technique based on sputter-initiated RIMS with time of flight MS described (40 pg kg-') Sample ignited at 500 "C and digested in HCl + HNO,. Au preconcentrated by extraction with 3-methylbutan-2-01 0.1-1 g of sample digested in HC1+ HNO + H2S04 + H,PO,.Thiourea and ascorbic acid added to mask interferences from Au Cu Se and Te and reduce the interference effects of As Hg and Sb. KBH used as reductant See As ref. 9411261 See As ref. 9411787 See As ref. 9412710 Effect of particle size and leakage of vacuum system Synchrotron radiation source microprobe used for on I3C and "0 investigated excitation. Ca Cl and K Cl ratios measured with an error of f30% Sample digested in HCl + HNO taken to dryness Si removed by evaporation with HF and H2S04 residue filtered off and fused with Na,CO and cooled melt dissolved in filtrate Study of heavy metal contamination in Lake Yojoa (Honduras) carried out Cd complexed with APDC and extracted with IBMK Optimized heating programs developed for 6-phase sequential extraction scheme See Ca ref.9412228 Method for high precision measurement of stable Cl Different types of inter-element interferences isotopes described affecting the estimation of the determinands were identified and eliminated using a two parameter theoretical model and single component calibration standards. Method validated on standard samples See Al ref.9411764 See Ag ref. 9412967 Single standard calibration carried out using FI sample introduction with an on-line dilution gradient. Sampling rate of 240 h-' with an RSD of < 3% achieved See Cd ref. 941361 94/36 1 See Co ref. 941758 941758 See Au ref. 9411650 9411650 See Cd ref.9412642 9412642 See Ag ref. 9412967 9412967 5 pg samples of oven dried powdered material 9412232 directly irradiated.Analytical method uses fast neutron activation involving the reaction 19F(n,a)'6N and gamma spectrometry ( 5 pg g-? See Al ref. 9411764 9411764 Fe203 used as stabilizer and a double internal 941146 standard used to correct for matrix effects. The RSD of the method was 4.3-13% Determinands extracted from sample solution with tri-butylphosphate followed by re-extraction into an aqueous phase Sampes digested in H,SO + H3P04 + HNO + HF. Hydride formed by mixing with 1% KBH (8.3 ng m1-I) 941949 9411097 Au Ore minerals SIMS;-;S Au Ore sample AA;F;L Au Geological materials 9412349 AA;F;L Au Au Minerals Ore RIMS;-;S AAETAL 9412665 9412805 Bi Geological samples AF;F,H y;L 941153 Bi Bi Bi C Geological sample Sediments Geochemical samples Carbonates A A;H y;L AEICP,Hy;L AF;-;L MS-*- 9 9411261 9411787 9412710 94/2824 Ca Synthetic fluid inclusions XRF;-;L 9412228 Ca Iron ore AA,F C,H,-N,O;L 9412605 Cd Lake sediments AA;F;L 941361 9411726 Cd Quaternary limestones AA;F;L Cd Sediments AA;ETA;L 9412642 Synthetic fluid inclusions Geological samples 9412228 9412237 c1 c1 c o Marine nodule samples AA;F;L 941758 Cr Cr c u Chromitites Estuarine sediment Arsenical pyrite AA;F;L AA;F air-C,H,;L AA;F;L 9411 764 9412967 941259 c u c u c u c u c u F Lake sediments Marine nodule samples Ore samples Sediments Estuarine sediment SRMs AA;F;L AA;F;L AA;F;L AA;ETA;L AA;F air-C,H,;L NAA;-;S AA;F;L AE;d.c. arc;S Fe Ga chromitites Ores AE;ICP;L Ga Zinc ores Ge Geological samples AF;Hy;L Journal of Analytical Atomic Spectrometry February 1995 Vol.10 37 RTable 4 (continued) Technique; atomization; analyte form* AA,CV;G Element Matrix Sample treatment/comments Reference Geological samples Sediment Samples extracted with aqua regia diluted and passed through a column packed with xanthate cotton followed by extraction with a smaller volume of aqua regia. SnC1 used as reducing agent Isotope dilution quantification used. Sample spiked with "'Hg followed by 1 h acid digestion. Quantitative recovery obtained for BEST- 1 sediment sample (2ng g-') Methyl mercury distilled from samples followed by aqueous phase ethylation precollection on a Carbotrap followed by isothermal GC prior to detection 9411 161 See As ref. 9411787 Sample acidified organo-Hg compounds extracted into toluene followed by gel-permeation chromatography clean-up and final separation of the compounds by GC Samples digested in HNO + HCl in sealed vessels.FI sample introduction used; Hg vapour formed by reduction with SnC1 NaBH reductant used (0.11 ngml-') See Ga ref.94/949 Determinands extracted from H,SO + HBr + KBr solution with IBMK. Zeeman effect background correction used Recoveries of 97.5-102.5% found See Na ref. 9411 155 See Ca ref. 9412228 Results compared to those previously obtained by NAA; differences between the results for the two methods discussed See Al ref. 9411764 Review of methods presented Samples digested in HF + HClO (2 + 1). Tartaric acid + KC1 + SrCl added to sample solution prior to analysis to remove interferences 615N values measured MS;ICP;L 9411283 Sediment AF;CV;G 9411 6 15 Sediments Marine sediment RMs AE;ICP,CV;L AE;CV.;G 9411787 94lC1965 AA;CV.; L 9412 5 92 Zinc ore concentrate Sediments Zinc ores Geochemical samples AA;CV;G AE;ICP;L AA,ETA;L 9412730 941949 9411151 Hg In In Fertilizers Ores Synthetic fluid inclusions Geological samples AA;F;L AA;F;L XRF;-;L RIMS;-$ 941946 9411 155 9412228 9412191 K K K Lu AA,F;L AA;F;L SI M S; -;S Chromitites Meteorites Rocks. nodules and soils 9411764 9412609 941759 MS;ETAG AA;F;L N Na Cornubian batholith (south Ores west England) 9411386 9411155 Samples digest in HN03 + HF and heated with H2S04 to remove F. Pulsed sample introduction system used associated with dolomites (e.g. halite gypsum anhydrite) followed by dissolution in HN03. C1 and SO4 also determined by ion chromatography.Samples digested in HF + HNO + HCl. 95Mo and lS5Re used as internal standards (Nb 40 ng g-' Ta 0.8 ng g-') mixtures of HF + HNO + HC104 and HF + HNO + H3B04 and evaporated to dryness. Residue moistened with HCI and tartaric acid and taken into solution. Cupferron used to preconcentrate determinands Samples leached to remove soluble salts not 0.5-1 pg of sample treated with HF followed by '43Nd/'44Nd ratios measured Na Dolomites AE;DCP;L 9412226 MS;ICP;L Nb Silicate rocks 9412229 Geological materials AE;ICPL Nb 9412389 Nd Ni Geological Survey of Japan MS;-;- Geological samples AA,F;L RMs 9411 38 1 941149 0.5-1 pg of sample digested in HC1+ HNO + HC104 + HF. Ni complexed with dimethylglyoxime and extracted initially into an organic phase and finally into 5% HCl.No interferences observed for Cu Fe Mo Pb W and Zn (0.04 pg g-') without prior separation NH4V0 matrix modifier allows measurement See Co ref. 94/758 59Ni measured by accelerator MS See Cd ref.9412642 Ni precipitated on line with l-nitroso-2-napthol and dissolution of complex with C,H,OH. Presence of H,O enhanced Ni sensitivity and Tiron used to reduce Fe interference Accelerator MS used to measure 59Ni See C ref. 9412824 Ni Iron ore AA;ETAL 941206 Marine nodule samples Extraterrestrial matter Sediments Silicate rocks AA;F;L AA;ETA;L AA,F air-CzHz;L MS;-;S Ni Ni Ni Ni 941758 9411442 9412642 9412982 Ni 0 Meteorites Carbonates MS;-;- MS;-- 9412 7 34 9412824 38 R Journal of Analytical Atomic Spectrometry February 1995 Vol. 10Table 4 (continued) Technique; atomization; analyte form* Element Matrix Sample treatment/comments Reference 0 s Molybdenite Molybdenite MS;-;L Samples irradiated with thermal neutrons in a 9412235 nuclear reactor followed by negative TIMS. 0 s isotopic compositions before and after irradiation used to date sample M S;ICP;L Sample digested in a sealed vessel with 9412236 HNO + H$O followed by oxidation with K,Cr,O,.0 s distilled off as OsO and trapped in 0.1% thiourea. Re separated from matrix by ion exchange chromatography. ID quantification used. Results used to date sample See Cu ref. 941259 1 pg sample fused with 4 pg NaOH + 2 pg Na202 in Ni crucible at 700 "C for 15 min. Fusion dissolved in boiling H,O extracted with diphenylthiocarbazone tetrachloromethane and back extracted into 5% HC1 Nd YAG laser microprobe sample introduction used to measure '07Pb z06Pb ages in single grains See As ref.9411590 Samples also analysed by differential pulse ASV Laser ablation sampling used. '"Pb '06Pb ratios See Cd ref. 9412642 Palladium nitrate matrix modifier used; results compared well with those from conventional digestion sample preparation minerals containing significant amounts of Fe described '07Pb 206Pb measured by direct evaporation on a double filament See Au ref. 941435 See Au ref. 941435 Comparison made between energy dispersive and See Os ref. 9412236 Review of different instrumental methods with 60 zlopb. .'06Pb ratios used to measure U-Pb ages used to measure U-Pb ages Method for the separation of U and Pb from wavelength dispersive methods refs.0 s Pb Pb Arsenical pyrite Phosphate mineral AA;F;L AA;F;L 941259 9411258 Pb Zircon MS;ICP;S 9411387 Pb Pb Pb Pb Marine sediment RM Sediments Zircons Single pitchblende and zircon grains Sediments Marine sediments XRF-;S AA;-;L MS;-;L MS;ICP;S 9411 590 9411786 9412225 9412227 Pb Pb AA;ETA;L AA;ETA;Sl 9412642 9412956 Pb Titanite and allanite MS;-;- 9412 73 8 Pb Single zircon grains MS;-;L 9412807 Pd Pt Rb Soils and sediments Soils and sediments Silicate rocks AAETA;L AA;ETA;L XRF;-;S 941435 94/43 5 941299 Re REE Molybdenite Geological samples M S;ICP;L AA;-;- AE;-;- MS;-;- NAA;-;- XRF;-;S MS;ICP;S 9412236 941204 REE Clinop yroxene Laser ablation microprobe operated at 266 nm used for sample introduction. Dual flow gas system allowed aqueous standards to be used for calibration.Detection limits and selectivity found to be superior to those using electron microprobe (100 Clglkg) Different dissolution procedures compared and showed significantly different values. Ultrasonic nebulization used Optimized ion-exchange procedure described using Dowex 50 X8 cation-exchange resin column. Eluate concentrated and introduced using an ultrasonic nebulizer Samples dissolved in hot concentrated H,SO 941292 REE REE Phosphates and sedimentary AE;ICP;L rocks 941599 9411078 Geological materials AE; I C P; L REE REE Phosphate minerals Geological samples AE;ICP;L AE;ICP;L MS;ICP;L 9411 117 94f 1182 Samples digested in HClO + HF taken to dryness and redissolved in HC1. REEs separated using a novel countercurrent chromatography system based on the retention of the stationary phase of a two-phase liquid system in a rotating column under the action of centrifugal forces while the mobile liquid phase is pumped through Rocks and sediment RMs MS;ICP;L In used as internal standard 9411373 Tholeiitic and calc-alkaline AE;ICP;L REE data used to provenance different rock types 9411763 Monominerals _- .. 9 Separation procedure described using P 507 9412 170 Fluid inclusions MS;ICP;L Samples prepared by crush leach method 9412233 Geological samples AE;ICP;L Samples digested by either acid digestion or alkali 9412279 magma extractive resin and 732 ion-exchange resin fusion. Three methods used for preconcentration (i) precipitation of hydroxides; (ii) TLC; (iii) LC. Method (iii) found to be most effective (0.1-100 pg) Rock soil and river sediment XRF;-;S Pressed powder sample preparation used 9412290 REE REE REE REE REE REE Journal of Analytical Atomic Spectrometry February 1995 Vol.10 39RTable 4 (continued) Technique; atomization; analyte form* AE;ICP;L Sample treatment/comments Samples decomposed in dilute HNO,; insoluble residue fused with Na,C03 a mixture of Na2C0 + Na,B,O or LiBO Synchrotron microprobe used Samples from Broken Hill Pb-Zn-Ag ore-bodies from Australia analysed Compilation of data from 235 laboratories Reference 9411731 9412527 9412607 9412634 9412962 941269 1 9411797 9411797 9412223 941 1 2 6 1 9411782 9411787 94/27 10 9411200 Element REE REE REE REE REE REE Rh Ru Ru Sb Sb Sb Sb Se Matrix Ores Geological samples Garnet and garnetite Geological Survey of Japan Rocks RMs Samples digested in K2C03 or K2B407; K and B removed from solution prior to analysis to reduce dissolved salts content Setting up of method using ID calibration described Thermal atomization of a substance in vacuum combined with RIMS described (TARIS) See Rh ref.9411797 MS;ICP;L MS;-;L RIMS;-$ Geological samples Geological deposits and rock samples Geological deposits and rock samples Uraninite Geological samples Chemical exploration samples Sediments Geochemical samples Geochemical samples RIMS;-$ See Ag ref. 9412223 See As ref. 9411261 See As ref. 9411782 MS;ETA;L AA;Hy;L AF;-;L See As ref. 9411787 See As ref. 9412710 Samples digested with HN03+HC1 in an autoclave at 200°C. Digest diluted adjusted to pH 2 and warmed with 15-20 pg of POLYORGS XXII sorbent to remove the Se.Sorbent filtered and suspended in water prior to analysis (2 ng g-') C1 isobaric interferences removed by using tubular membrane gas-liquid separator Sediment spiked with tributyltin equilibrated for 10 d and extracted with an optimized mixture of HCl+ MeOH GC used to separate organotin compounds prior to AA quantification HPLC used separate organotin compounds prior to AA quantification. Tributyltin and dibutyltin detected down to a few ng g-'. Monobutyltin strongly retained terabutyltin not separated from tributyltin GC used to separate organotin compounds prior to AA quantification. Sediments extracted with methanolic HCl or methanolic NaOH. Ethylated tin compounds generated with sodium tetraehylborate collected in N2 cold trap prior to separation (mono- di- and tributyltin 9 38 and 12 kg-9 GC separation used to separate organotin compounds prior to detection.Poor recoveries found to be due to inhibition of hydride generation and not atomization interferences acid +thiourea + NH pyrolidinedithiocarbamate. Solution extracted with IBMK. Sample reduced with ethanolic NaBH to produce SnH Sample solution mixed with HNO +tartaric See Rb ref. 941299 Sample digested in HNO + HClO + HF taken to near dryness and finally dissolved in NH,EDTA as a matrix modifier See Nb ref. 9412229 See Nb ref. 9412389 See Ag ref. 9412223 High precision method for measuring Th isotope ratios using continuous wave lasers described Silicates digested in HNO + HF and Fe meteorites with HNO,.Digest mixed with KI + K,HPO and the iodo complex extacted into IBMK (2 ng g-') See In ref. 9411 151 See Pb ref. 9412738 Sample digested in HCl + HNO + HF taken to dryness redissolved in HC1+ H3BO4 filtered and residue fused with Na2C03 and cooled melt dissolved in filtrate. For low levels solvent extraction preconcentration used See Cu ref. 94/259 See Cd ref. 941361 AE;ICP Hy;L AA;ETA;Sl AF;-;L Se Sn Sediments Rhine river sediment 9412750 941486 MS;ICP Hy;L AA;- Hy;L AA;F;G AA;ETA;L 941487 941488 Sn Sn Sediments Sediment Sn River sediments AA,ETA;G 94/39 AA;ETA Hy;L Sn River sediment 941786 Sn Geochemical prospecting samples AA;F air-C,H HY;L 9411 162 XRF;-;S AA,ETA;L Sr Sr Silicate rocks Sediment 941299 9411154 Silicate rocks Geological materials Uraninite Geochemical samples MS;ICP;L AE;ICP;L MS;ETA;L RIMS;-$ 94 f2229 9412389 9412223 9412830 Ta Ta Te Th Rocks and meteorites AA;ETA;L 941636 T1 T1 U V Geochemical samples Titanite and allanite Iron ore AAETA;L AA;F MS;-;- C2HZ-NlO;L 9411151 9412738 9412606 AA;F;L AA;F;L Zn Arsenical pyrite Zn Lake sediments 941259 9413 6 1 40 R Journal of Analytical Atomic Spectrometry February 1995 Vol.10Table 4 (continued) Technique; atomization; analyte form* AE;ICP;L AE;ICP;L Sample treatmentlcomments See Cu ref.1206 Tributyl-phosphate extraction chromatography used to extract impurity elements from matrix. Samples proposed as CRMs Products of samples pyrolysis separated on a gas chromatographic column prior to detection Ag As Au Pb and Sb used as pathfinder elements for Au prospecting.Reference 9411 206 941 14 9416 1 94/69 94/74 94/76 94/96 Element Matrix Zn Sediments Various u3os Various Geochemical samples AE;MIP;G AE;dc arc$ AE;ICP;L AE;ICP;L Various Stream sediment soil rock fragments heavy mineral concentrates Various Soils and sediments Samples digested in HF + HNO + HClO taken to dryness and redissolved in 50% HC1. Instrumental parameters were optimized and spectral interferences investigated Elemental compositions (Co,Cu Fe Mn Ni and Zn) compared with mineralogical abundances Be Ce Co Cr Cu La Li Mo Nb Ni Pb Sn Ti V Y and Zr used as pathfinder elements in geochemical exploration for atomic minerals. Method showed good agreement with results by ICP-AES XRF and INAA Review with 673 refs. Various Fine fractions of till Various Geochemical exploration samples AA;F;L AE;dc arc$ Various Various Various Various Various Rocks and minerals 94/99 941103 941140 941159 941165 Silicates Modifications to enable a proprietry fusion unit to handle samples containing high Al Fe and Si more effectively are described AA and IR absorption spectroscopy used to study impurties in quartz.Amongst others elements Al Na and Li investigated Chemical and minralogical analysis used to identify sample Synthetic quartz and Brazilian natural quartz AA;-;- XRF;-;S NAA;-;S AE;ICP;L Iron meteorite Geological materials Quality control procedure for measuring Be Co Cu Ni Sc V Y and Zr described. Protocol uses control check solutions SRM solutions and in house standards to give an overall precision of f2-5% RSD with an accuracy of 5% A review of methodologies with 9 refs.16 trace elements determined by dc arc emission and Au by AA. Structural and trace element chracteristics of sample related to its Au bearing potential Review with 103 refs. Review on the use of microwave digestion with 47 refs. 247 RMs accredited in China described Review with 9 refs. Various Various River sediment Quartz AA;ETA;Sl AA;-;L AE;dc arc$ 9411 80 941198 XRF-;S -._*- Y . . _- AE;ICP;- XRF;-;S MS;ICP;- Various Various Various Various Geological samples Geological samples Geologcal RMs Geological samples 94/201 94/202 941203 94/205 Used a variable sample to flux ratio allowing flux to be dipensed by volume promoting rapid sampling. Variations in flux content corrected by solving a system of equations HC1 in 150 ml PTFE container left for 10 min and screw capped.Sample microwaved for 1 min at 540 W and 1 h at 300 W. Residue filtered fused with Na2C03 + Na2B,0 (3 + 1 ) dissolved in 2 moll - ' HCl and combined with original filtrate Acid dissolution and alkali fusion attacks compared; the latter found to give more accurate Si values. Al Cr Fe Mg and Mn also determined techniques with 107 refs. 500 pg of sample treated with 20 ml of 12 moll-' Review of developments of mineral analytical 9413 3 3 Various Silicate materials 941370 Various Geological samples AE;ICP;L 94/46 1 941539 941564 Various Various Chromi te Minerals AE;ICP;L AA;-;- AE;ICP- XRF;-;S N AA; - ; S MS;ICP;L Oxychlorine atoms of alkali earth elements shown to exist in mass spectra of rock solutions containing HClO,.Evidence given that polyatomic ions are related to speciation in the sample and not entirely formed in expansion stage of ICP-MS Samples sawn and etched with HNO + HCl + H20 ( 1 + 3 +4) for 1-10 min and rinsed with H,O and acetone. Element concentrations and isotope abundances determined Various Rock materials Various Iron meteorites MS;GD;S 941567 Journal of Analytical Atomic Spectrometry February 1995 Vol. 10 41 RTable 4 (continued) Technique; atomization; analyte form* AE;ICP;Sl Sample treatment/comments Reference Element Matrix Various Geological samples Micrometre to submicrometre particles obtained using zirconia bead and bottle method. V-groove nebulizer used for sample introduction. Combinations of aqueous standards matched RMs and correction factors used to calibrate and quantify results FI system with stopped flow microwave reactor used to digest SRMs.Slurry samples injected into manifold and flushed into glass reactor in a microwave oven along with HNO,. Sample heated for 5 min at 400 lb inp2 pressure 0.3 pg of sample digested in HF + HNO + HClO,. After dilution In carrier added followed by NH3 solution and thioacetimide to precipitate the sulfide. Precipitate washed and dissolved in aqua regia Review of literature from Nov. 1990 to Oct 1992 941570 941578 Coal AA;F;L Various AE;ICP;L 9417 1 7 Various Calcite Varoius Geological materials 94/77 1 Esturine sediment Soils and minerals Sample dissolved in HNO,. Smith-Hieftje background correction gave better results than deuterium arc or no background correction. Cu Fe Mn and Zn determined simultaneously Samples prepared as 1% aqueous slurries using conditions similar to aqueous solutions.Results affected by sample type and chemical form of determinand. Se lost during thermal pretreatment stage. As Cd Pb and V also studied with Zeeman background correction used in real time to obtain continuously updated quantitative analyses as data accumulate Metal pollution in sediments and suspended matter from Belgian North Sea and the Scheldt Estuary investigated Data from laser ablation sample introduction of MnO coatings of pebbles used as a geochemical surveying method to identify mineralized areas Al Co Cr Cu Fe Mn Ni Pb and Zn determined in aqua regia extracts. 189 sites in 52 Quebec and Ontario lakes sampled determination of platinum group elements using collection into a minimized NiS button investigated EDXRF used to determine 22 trace elements using 55Fe '"Cd and 241Am sources 1% slurry in 10% HNO analysed giving recoveries of 40-70% against aqueous standards. Standard addition calibration gave results within 5% of certified value for Cd Cu Fe and Zn Sample digested in HNO,+HClO,+HF.Be Cr Ge Mo V and Zr analysed (0.038 0.030 0,110 0.015 0.030 and 0.024 repectively) Samples analysed with synchrotron X-ray microprobe Powdered samples fused with Li,B,O? + Li2C03 + LiNO,. Cu Mo Pb Zn and W determined anion-exchange columns and eluted with 0.5 mol 1-l NH4Cl and 3 mol 1-' NH,. As Cr Mo S and Se determined (13 3.64 2.04 6.19 and 25.2 ng ml-l respectively) Recovery of precious metals (except Au and 0 s ) following NiS fire assay improved by dissolution of assay beads using sealed Teflon vessels and co-precipitation of the determinands with tellurium carrier Samples pulverized and directly pressed into pellets.Detection limits for Ba Co Cr Cu Ni Rb Sn V and Zn 9.5 3.0 3.5 2.2 2.6 2.8 1.8 4.2 and 2.4 pg g-' respectively Accelerator MS system used; results semiquantitative due to matrix effects. Sub ng g-' detection limits obtained on microgram quantities of sample Spectral decomposition transform developed to be Effects of fusion charge composition on the On-line FI preconcentration using parallel D296 941778 94/794 Various A A;ETAS Various Various Minerals PIXE;-;S 941904 Various Sediments AA;F;L XRF;-;S 941928 Various Stream sediment pebble coatings AE;ICP;S 941940 AA;F;L 941944 Various Surficial sediments Various Geological samples AA;ETA;L 941986 Various Marble Various Marine sediments XRF;-;S AE;MIP;Sl 94/99 1 9411 010 Various Geological RM AE;MIP;L 9411 153 Various Geological SRMs Various Non-ferrous metallic ores 941 1 1 56 9411 157 Various Geological samples AE;ICPL 94/72 1 Various Geological samples MS;ICP;L 9411 177 Various Oil shale Various Sulfide concentrates 9411 2 16 9411 356 42 R Journal of Analytical Atomic Spectrometry February 1995 Vol.10Table 4 (continued) Technique; atomization; analyte form* MS;ICP;L MS;-;S Element Matrix Various Minerals Sample treatment/comments Nd YAG laser ablation sample introduction system operated at 1064 nm used (0.5 pg g-') Platinum group elements and Au determined by accelerator MS Nd:YAG laser ablation sample introduction system used on pressed powder pellets.Results for the analysis of SRMs and various calibration strategies given 37 trace elements including REEs determined in 28 SRMs. Samples either digested in HF + HC104 + HN03 + HCI in pressure bomb or by LiB40 fusion. Agreement with certified values good apart from low values for light REEs application with 28 refs. system used scintillation counter described Review of the use of the method for geochronologcal Synchrotron radiation source with ED detection Inexpensive and high performance gas proportional 22 samples from Portugal and Thailand analysed Samples digested in HF + aqua regia. Elements preconcentrated by ion-exchange chromatography.Instrument able to measure all elements simultaneously and used Zeeman effect background correction. Ag Au Ir Pd Pt Rh and Ru determined Review of methodologies for geochemical analysis of sediments Five operationally defined fractions separated and analysed for Cd Co Cr Cu Fe Mn Ni Pb and Zn Characterization of the sediments types carried out by the different AS methods Reference 941 13 57 9411 3 59 9411364 9411382 Various Sulfide minerals Various Geological SRMs MS;ICP;S Various Geological SRMs M S;ICP;L Various Geological RIMS;-; - 9411489 Various Light silicate materials XRF;-;S 9411572 Various Biotite and pyrite/ chalcopyrite Marble Silicate rocks XRF;-;S 9411586 Various Various XRF;-;S AA;ETA;L 94/19 9411 648 Various Various Marine sediments Pacific ocean sediments AA;-;- 941 1 7 3 7 9411765 AA;F;L Various Various Baltic sea sediments AA;-;L AE;ICP;L EPXMA;-;S AA;L;F air-C,H N,O-C2H2 ;L AE;ICP;L AE;laser;S AF;ICP;L 9411845 Ore samples Traditional solution techniques compared to direct analysis of solids 94fC1877 Various Various Geological samples Geological Possiblities for different applications with FI sample Summary of the research and applications carried introduction discussed out in the last 25 years at the Geological Survey of Canada Automated sample preparation including use of Microdigest A300 and PERLX 2 proprietary instrumentation described Nd:YAG laser sample introduction system used on glass beads produced on a W-strip heater under an Ar atmosphere to suppress the loss of volatile elements and suppress oxidation.REE and trace metals analysed Ba Ca,Cr Cu Fe Mn Pb Rb Sr Ti and Zn determined in exchangeable metal fraction carbonate fraction Fe/Mn hydroxide fractions organic fraction and residual fraction obtained from a sequential extraction scheme. Samples irradiated with thermal neutrons followed by alkali fusion with carriers and acid dissolution activated metals and carriers concentrated by Te co-precipitation (0.01 pg kg-' Ir and Au 1.0 pg kg-' Pd 2.0 pg kg-l Pt and Ag and 5 pg kg-' Se As and Sb) As Ba Ce Co Cr Cs Cu Eu Ga Hf La Lu Nb Nd Ni Pb Rb Sb Sc Sm Sr Ta Tb Th U V W Y Yb Zn and Zr determined carried out paper. Results for 2 RMs agreed with certified values effects shown to be useful in predicting limitations in the micro-analysis of geological samples sample described Multi-element analysis of proposed IAEA RM 10 pg of powdered sample placed on ceellophane glue Monte Carlo simulation of the grain size and edge Description of preparation of and certification of 94/c 19 32 9412387 AA;F,ETA;L Various Glasses carbonates sand limestone dolomite and chromite Whole-rock glasses AE;ICP;L 9412 146 Various MS;ICP;S 9411363 Various Coastal sediments TXR F; - ;L 94/22 19 Various Sulfur poor ultramafic mafic NAA;-;S and sedimentary rocks 9412224 Various Japan igneous and sedimentary rock standards Coastal marine sediment INAA;-;S XRF;-;S 9412230 Various Various Various INAA;-;S 941223 1 941226 1 9412268 Montmorillonite XRF;-;S Geological samples XRF;-;S Various Venezuelan lateritic material 9412352 Journal of Analytical Atomic Spectrometry February 1995 Vol.10 43RTable 4 (continued) Element Various Various Various Various Various Various Various Various Various Various Various Various Various Various Matrix Surinam lateritic bauxite Sulfide-bearing CRMs Geochemical samples Rocks Silicate and carbonate raw materials Geological samples Geological samples Geological samples Zagami meteorite Rock forming minerals Silicate materials Aluminosilicate clays Environmental samples Geological samples Technique; atomization; analyte form* _._*_ * XRF;-;S MS;ICP;L AE;ICPL XRF;-;S XRF;-;S SI M S; - ;S AE;ICP;L MS;ICP;L XRF;-;S N A A; -;S MS;ICP;- XRF;-;S PIXE-;S MS;-;- Sample treatment/comments Description of preparation of and certification of !Samples prepared by oxidizing borate fusion; sample described calibration standards prepared from pure elements or their compounds with quality assured assays Historical perspective of advances in analytical technology and its influence on inorganic geochemistry concentrated by dry chlorination in the presence of of NaCl at 580°C and dissolution in 10% HCl Calibration drift minimized by maintaining the spray chamber at constant temperature.Samples fused with LiBO and dissolved in HNO !Samples analysed using synchrotron microprobe at Daresby Proposed modifications to existing fusion procedures included using different combinations of Li,B,O LiBO LiNO LiF and Li,CO Kulenkampff-Kramers formula used to correct for background under the analytical peak. Method used to determine Ba Ce Cs and La Platinum group elements and Au extracted and !Synchrotron microprobe used Review of methods for using stable isotope ratio measurements for studying diffusion kinetics 1 pg sample digested in PTFE bomb with 10 p1 H,S04+20 ml HF+ 6 ml HN03 at 150°C for 10 h.HF removed by heating solution to fumes. Sc used as internal standard for ICP-MS. Preconcentration of determinands by ion-exchange chromatography carried out prior to ICP-AES analysis microcrystalline cellulose binder used. Al Ca Fe K Si and Ti determined techniques with 18 refs. Pressed powder pellets of samples mixed with Review of nuclear and nuclear related analytical Review of the progress in isotope MS and inorganic MS in China during 1991-1992 with 252 refs. Reference 9412353 9412357 9412374 94/23 86 9412390 9412446 9412474 9412475 9412483 94/26 10 9412564 9412695 94/28 16 9412 8 2 5 - * Hy indicates hydride and S L G and S1 signify solid liquid gaseous or slurry sample introduction respectively.Other abbreviations are listed elsewhere. t Values in parentheses are detection limits. The versatility of glow discharge mass spectrometry was put to good use for the multi-element and isotopic analysis of iron meteorites (94/567). Virtually all elements can be determined from major elements (Co Fe Ni) through to ultra-trace constituents at the sub-ng g-' level. The successful use of mass spectrometry for the precise measurement of zloPb 'O'Pb ratios in zircons was described by Wendt et al. (94/2225) who used this system to determine U-Pb ages solely by measuring lead isotopes.The very low (lo-') ratios measured necessitated the use of a high abun- dance sensitivity lens system. Good agreement was obtained with conventional U-Pb age determinations using ID methods. 4.3.6. X-ray methods There seems to be a slight resurgence in the number of papers using X-ray methods of analysis during the past year although whether this is due to increased research activity or more efficient reporting methods is difficult to judge. Increased awareness of the advantages of micro-analysis has produced a number of studies based on the use of synchrotron X-ray fluorescence (SXRF ). Chen et al. (94/2527) determined REE in both singIe mineraI grains and synthetic samples by using the REE Ka lines. Detection limits ranging from 6 pg g-' (La) to 29 pg 8-l (Lu) were obtained from a 60 pm sample.The same techhnique was used to determine the concentrations of Au Nb Ta TI and W in lepidolites from Portugal (94/1572) and also several trace elements in geological samples (94/2446). Synthetic fluid inclusions as small as 10 pm in quartz were analysed by SXRF and measured ratios of Ca C1 and K Cl were within 30% of the nominal value (94/2228). Sometimes results have to be treated with caution owing to variations in particle geometry. Lanksoz (94/2268) adapted a Monte Carlo method previously used with spherical particles for use with cylindrical particles. His approach enabled limitations in the microanalysis of geological samples to be predicted. Another useful microanalysis technique is particle induced X-ray emission (PIXE) which requires a continuous feedback of results in order to monitor changing zoning profiles or detect inclusions present in the sample.Ryan and Jamieson (94/904) reported the development of a dynamic analysis technique which continuously updates quantitative PIXE analyses. The use of this system enabled the true distribution of Au in pyrite to be determined by rejecting interferences from As and Zn. Investigations into reference materials using both EDXRF and WDXRF have been the subject of several papers. Polish workers (94/1590) were able to determine simultaneously trace amounts of As and Pb in a marine sediment RM SD-M- 2/TM using EDXRF. The use of an emission -transmission measuring technique enabled overlapping AsKa and PbLcc 44R Journal of Analytical Atomic Spectrometry February 199.5 Vol. 10peaks to be deconvoluted.Staats and Strieder (94/2357) vali- dated 5 sulfide-bearing RMs after using an oxidizing borate fusion to prepare samples for analysis by WDXRF. The concentrations of major and trace elements in these RMs were determined from a multi-element calibration curve. Webb et al. (94/299) carried out a comprehensive study into the precision of Rb and Sr determinations in silicate RMs by both EDXRF and WDXRF. They concluded that for amounts <20 pg g-' both methods gave similar precision but at higher concen- trations the use of WDXRF was preferable. Three radioactive sources 241Am lo9Cd and "Fe were used for the irradiation of marble pieces before analysis by EDXRF (94/19).This method enabled As Cu Fe Mn Sr Y and Zn to be determined and the source of the marble was established by plotting the concentrations of Fe Sr and Y on a triangu- lar diagram. 4.3.7. Neutron activation analysis Reported applications of NAA have been somewhat scarce this year. A notable exception was a paper by Stone and Crocket (94/2224) who employed thermal neutron irradiation of samples followed by alkali fusion and Te coprecipitation to determine Ag As Au Ir Pd Pt Sb and Se to sub-ng g-' amounts in mafic/ultramafic rocks. Analysis of the gamma ray spectra produced gave an estimated LOD of 0.1 ng 8-l for Au and Ir 1.0 ng g-' for Pd 2.0 ng g-' for Ag and Pt and 5 ng 8-l for As Sb and Se. Several reference materials have been analysed using NAA techniques.Fluorine was determined in 29 RMs using fast neutron activation involving the reaction '9F(n,a)-+16N + y with measurement of the gamma rays produced (94/2232) and instrumental NAA was used to determine 32 elements in a marine sediment RM (94/2231). Hallett and Kyle (94/2230) compared XRF and instrumental NAA for the determination of 23 trace elements in 12 Japanese RMs. LOCATION OF REFERENCES The full list of references cited in this Update have been published as follows 94/1-94/614 J. Anal. At. Spectrom. 1994 9( l ) 1R-23R. 94/61 5-94/960 J. Anal. At. Spectrom. 1994,9(2) 73R-85R. 94/961-94/1264 J. Anal. At. Spectrorn. 1994 9(4) 135R-146R. 94/1265-94/1830 J. Anal. At. Spectrom. 1994 9( 5 ) 149R-169R. 94/1831-94/2175 J. Anal. At. Spectrom. 1994 9(6) 189R-200R.94/2176-94/2412 J. Anal. At. Spectrorn. 1994,9(7) 203R-212R. 94/2413-94/2867 J. Anal. At. Spectrom. 1994 9( 8) 249R-265R. 94/2868-94/2994 J. Anal. At. Spectrom. 1994 9( lo) 307R-3 12R. Abbreviated forms of the literature references quoted (excluding those to Conference Proceedings) are given on the following pages for the convenience of the readers. The full references names and addresses of the authors and details of the Conference presentations can be found in the appropriate issues of JAAS cited above. Abbreviated List of References Cited in Update 9412 Adv. X-Ray Anal. 1992 35B 1047. 9419 Anal. Chem. 1993 65 1273. 94/11 Anal. Chim. Acta 1992 270 205. 94/14 Anal. Chim. Acta 1993,274,237. 94/15 Anal. Chim. Acta 1993 274 243. 94/16 Anal. Chim. Acta 1993 276 47.94/17 Anal. Chim. Acta 1993 276 173. 94/19 Appl. Spectrosc. 1993 47 300.94122 Bunseki Kagaku 1993,42,107.94/24 Fenxi Huaxue 1993 21 11. 94/25 Fenxi Huaxue 1993 21 187. 94/34 Fresenius' J. Anal. Chem. 1993 345 221. 94/35 Fresenius' J. Anal. Chem. 1993 345 227. 94/39 J. Anal. At. Spectrom. 1993 8 119. 94/44 Spectrochim. Acta Part B 1993 48 171. 94/45 Spectrochim. Acta Part B 1993,48 193.94154 Zh. Anal. Khim. 1993 48 73. 94/55 Acta Chim. Hung. 1992 129 611. 94/58 Agrochemia (Bratislava) 1992 32 298. 94/59 Am. Ind. Hyg. Assoc. J. 1992 53 290. 94/61 Anal. Proc. 1993 30 87. 94/65 Anal. Sci. 1992 8 533. 94/69 Appl. Geochem. 1992 7 533. 94/71 Atmos. Enuiron. Part A 1993 27 397. 94/74 Bol. SOC. Esp. Ceram. Vidrio 1992 31 219. 94/75 Bull. Chem. SOC. Jpn. 1992 65 1165. 94/76 Bull.Geol. SOC. Finl. 1992 64 59. 94/77 Bunko Kenkyu 1992 41 265. 94/83 Chem. Anal. (Warsaw) 1992,37,437.94/85 Chem. Listy 1993,87,64.94/86 Chem. Pap. 1992 46 385. 94/92 Environ. Sci. Technol. 1993 27 827. 94/96 Explor. Res. At. Miner. 1990 3 169. 94/99 Fenxi Shiyanshi 1992 11 98. 94/103 Fenxi Yiqi 1993 1 63. 941104 Food Chem. 1992 44 309. 941115 Guangpuxue Yu Guangpu Fenxi 1992 12 59. 941116 Guangpuxue Yu Guangpu Fenxi 1992 12 67. 941124 Int. J. Environ. Health Res. 1993 3 2. 94/128 J. AOAC Int. 1992 75 949. 941129 J. AOAC Int. 1992 75 1029. 941132 J. Environ. Qual. 1993 22 1. 941133 J. Flow Injection Anal. 1992,9 195. 941140 Jpn. J. Appl. Phys. Part I 1993 32 893. 941143 Kogyo Yosui 1992 409 83. 941144 Kogyo Yosui 1992 409 88. 941146 Lihua Jianyan Huaxue Fence 1992 28 224.941149 Lihua Jianyan Huaxue Fence 1992 28 351. 941153 Lihua Jianyan Huaxue Fence 1992 28 369 371. 941159 Meteoritics 1992 27 467. 941160 Mikrochim. Acta 1992,108,241.94/161 Mikrochim. Acta 1993 110,89.94/165 Nippon Sanso Giho 1992,11,31.94/166 Nippon Shokuhin Kogyo Gakkaishi 1992 39 984. 941168 Nucleon (Rez Czech.) 1992 4 14. 941178 PSI-Ber. 1992 129 89pp. 941179 Punsok Kwahak 1988 1 203. 941180 Quim. I d . (Madrid) 1992 38 526. 941186 Shanghai Huanjing Kexue 1992 11 26. 941188 Shenyang Yaoxueyuan Xuebao 1992 9 164. 941190 Shokuhin Eiseigaku Zasshi 1993 34 25. 941191 Silic. Ind. 1992 57 123. 941193 Staub Reinhalt. Luft 1993 53 27. 941196 Toxicol. Methods 1993 3 25. 941198 Vestn. Mosk. Univ. Ser. 4 Geol. 1992 1 48. 941200 Water Air Soil Pollut. 1993 66 111.941201 Yankuang Ceshi 1992 11 37. 941202 Yankuang Ceshi 1992 11 87. 941203 Yankuang Ceshi 1992 11,130.94/204 Yankuang Ceshi 1992,11,173.94/205 Yankuang Journal of Analytical Atomic Spectrometry February 1995 Vol. 10 45RCeshi 1992 11 197. 941206 Yejin Fenxi 1992 12 18. 941208 Yejin Fenxi 1992 12 48. 941209 Yejin Fenxi 1992 12 4. 941212 Yejin Fenxi 1992,12,30.94/217 Zavod. Lab. 1992,58 30.941218 Zavod. Lab. 1992,58,60.94/225 Anal. Chem. 1993 65 653. 941226 Anal. Chim. Acta 1992 267 31. 941227 Anal. Chim. Acta 1992 267 131. 941231 Anal. Chim. Acta 1992 268 177. 941234 Anal. Chim. Acta 1992 270 79. 941235 Anal. Chim. Acta 1992,270 87. 941238 Anal. Chim. Acta 1992,270 231. 941240 Anal. Chim. Acta 1993 272 91. 941241 Anal. Chim. Acta 1993 272 105. 941245 Analyst 1992 117 1953.941252 At. Spectrosc. 1993 14,47. 941253 At. Spectrosc. 1993 14 50. 941258 Fenxi Huaxue 1992 20 1227. 941259 Fenxi Huaxue 1992,20 1269.941261 Fenxi Huaxue 1992,20 1321. 941262 Fresenius’ J. Anal. Chem. 1992 344 301. 941263 Fresenius’ J. Anal. Chem. 1992 344 319. 941265 Fresenius’ J. Anal. Chem. 1992 344 340. 941271 Fresenius’ J. Anal. Chem. 1993 345 60. 941275 J. Anal. At. Spectrom. 1992 7 1239. 941283 J. Anal. At. Spectrom. 1993 8 229. 941284 J. Anal. At. Spectrom. 1993 8 235. 941290 J. Anal. At. Spectrom. 1993 8 279. 941292 J. Anal. At. Spectrom. 1993 8 299. 941299 J. Anal. At. Spectrom. 1993,8,293.94/301 J. Anal. At. Spectrom. 1993 8 379. 941324 Talanta 1992 39 1471. 941325 Talanta 1992,39 1517. 941327 Talanta 1992,39 1537. 941328 Talanta 1992 39 1643.941331 Zh. Anal. Khim. 1992 47 1405. 941333 Zh. Anal. Khim. 1992 47 1709. 941342 Am. Lab. (Shelton Conn.) 1992 24 42. 941346 Anal. Sci. 1992 8 851. 941348 Anal. Sci. 1992 8 863. 941350 Anal. Sci. 1992 8 893. 941355 Analusis 1992 20 561. 941358 Atmos. Environ. Part A 1992 26 3207. 941361 Bull. Environ. Contam. Toxicol. 1993 50 253. 941369 Chem. Anal. (Warsaw) 1992 37 635. 941370 Chem. Listy 1992 86 143. 941375 Chemosphere 1992 24 1077. 941376 Chin. Chem. Lett. 1992 3 915. 941380 Commun. Soil Sci. Plant Anal. 1992 23 2479. 941381 Commun. Soil Sci. Plant Anal. 1992 23 2525. 941382 Commun. Soil Sci. Plant Anal. 1992 23 2667. 941383 Crit. Rev. Anal. Chem. 1992 23 1. 941384 Dokl. Akad. Nauk 1992 323 939. 941385 Dokl. Akad. Nauk 1992 325 967. 941387 Environ.Technol. 1992 13 657. 941388 Fenxi Huaxue 1992 20 1231. 94/395 Gaodeng Xuexiao Huaxue Xuebao 1992 13 898. 941396 Gaodeng Xuexiao Huaxue Xuebao 1992,13,1057.94/413 ICP I n + Newsl. 1992 18 135. 941415 Indian J. Pure Appl. Phys. 1992,31,63.94/435 J. Geochem. Explor. 1992,46 187.941456 Jpn. J. Phycol. 1992 40 229. 941458 Khim. Tekhnol. Vody 1992,14,813.94/459 Latv. Kim. Z. 1992,6,702.94/461 Lihua Jianyan Huaxue Fence 1992,28,80,82.94/463 Lihua Jianyan Huaxue Fence 1992 28 173. 941465 Lihua Jianyan Huaxue Fence 1992 28 179. 941480 Mikrochim. Acta 1992 109 23. 941481 Mikrochim. Acta 1992 109 27. 941482 Mikrochim. Acta 1992 109 35. 941485 Mikrochim. Acta 1992 109 61. 941486 Mikrochim. Acta 1992 109 67. 941487 Mikrochim. Acta 1992 109 79. 941488 Mikrochim. Acta 1992 109 83.941491 Mikrochim. Acta 1992 109 149. 941492 Mikrochim. Acta 1992 109 107. 941493 Mikrochim. Acta 1992 109 201. 941495 Mikrochim. Acta 1992 109 243. 941518 Rud. Metal. Zb. 1992 39 93. 941519 Shokuhin Eiseigaku Zasshi 1992 33 359. 941532 Toxicol. Environ. Chem. 1992 36 205. 941538 Water Supply 1992 10 21. 941539 Yankuang Ceshi 1992 11 121.941552 J. Anal. At. Spectrom. 1993,8,269. 941553 J. Anal. At. Spectrom. 1993,8 325. 941559 J. Anal. At. Spectrom. 1993 8 409. 941560 J. Anal. At. Spectrom. 1993 8 415. 941564 J. Anal. At. Spectrom. 1993 8 439. 941566 J. Anal. At. Spectrom. 1993 8 449 941567 J. Anal. At. Spectrom. 1993 8 453. 941568 J Anal. At. Spectrom. 1993,8,461. 941570 J. Anal. At. Spectrom. 1993,8 475. 941577 J. Anal. At. Spectrom. 1993 8 691. 941578 J.Anal. At. Spectrom. 1993 8 687. 941582 J. Anal. At. Spectrom. 1993 8 723. 941585 J. Anal. At. Spectrom. 1993 8 745. 941597 J. Anal. At. Spectrom. 1993 8 821. 941599 J. Anal. At. Spectrom. 1993,8 833. 941606 J. Anal. At. Spectrom. 1993,8 875. 941613 J. Anal. At. Spectrom. 1993 8,921.941616 Spectrochim. Acta Part B 1993,48,977.94/636 Anal. Chim. Acta 1992 266 127. 941637 Anal. Chim. Acta 1992 268 315. 941641 At. Spectrosc. 1993 14 76. 941645 Fenxi Huaxue 1992,20,1288.94/649 Fresenius’ J. Anal. Chem. 1993 345 261. 941655 Spectrochim. Acta Part B 1993 48 183. 941657 Spectrochim. Acta Part B 1993 48 207. 941658 Spectrochim. Acta Part B 1993 48 223. 941659 Spectrochim. Acta Part B 1993 48 231. 941664 Talanta 1993 40 409. 941671 Food Chem. 1992 45 145. 941685 Mikrochim. Acta 1993 110 41.941691 Zavod. Lab. 1992 58 6. 941695 Anal. Chem. 1993 65 2096. 941707 Anal. Chim. Acta 1993 278 99. 941715 Bunseki Kagaku 1993,42 T57.941717 Bunseki Kagaku 1993 42 305. 941719 Bunseki Kagaku 1993 42 325. 941720 Fenxi Huaxue 1993 21 303. 941721 Fenxi Huaxue 1993 21 328. 941730 Fresenius’ J. Anal. Chem. 1993 345 467. 941755 Talanta 1993 40 221. 941758 Talanta 1993 40 675. 941759 Talanta 1993 40 701. 941760 Talanta 1993 40 729. 941765 Fresenius’ J. Anal. Chem. 1993 345 570. 941771 Anal. Chem. 1993 65 12. 941775 Anal. Sci. 1993 9 273. 941778 Anal. Lett. 1993 26 709. 941779 Anal. Lett. 1993 26 965. 941784 Appl. Environ. Microbiol. 1993 59 1274. 941786 Appl. Organomet. Chem. 1993 7 149. 941794 Appl. Zeeman Graphite Furn. At. Absorpt. Spectrom.Chem. Lab. Toxicol. eds. Minoia C. and Caroli S. Pergamon Oxford 1992 pp. 79-94. 941795 Appl. Zeeman Graphite Furn. At. Absorpt. Spectrom. Chem. Lab. Toxicol. eds. Minoia C. and Caroli S. Pergamon Oxford 1992 pp. 143-164. 941796 Appl. Zeeman Graphite Furn. At. Absorpt. Spectrom. Chem. Lab. Toxicol. eds. Minoia C. and Caroli S. Pergamon Oxford 1992 pp. 165-177. 941797 Appl. Zeeman Graphite Furn. At. Absorpt. Spectrom. Chem. Lab. Toxicol. eds. Minoia C. and Caroli S. Pergamon Oxford 1992 pp. 209-226. 941831 Environ. Technol. 1993 14 167. 941837 Fresenius’ Environ. Bull. 1992,1,499.94/838 Fresenius’ Environ. Bull. 1992 1 741. 941841 Gen. Tech. Rep. NC (North Cent. For Exp. Stn.) 1992 150 73. 941845 Guangpuxue Yu Guangpu Fenxi 1992 12(4) 71.941852 Indian J. Environ.Prot. 1992 12 324. 941853 Indian J. Environ. Prot. 1992 12 733. 941854 J. Aerosol Sci. 1992 23 S417. 941856 J. Am. Water Works ASSOC. 1993 85 77. 941864 J. Geochem. Explor. 1993 46 279. 941865 J. Geochem. Explor. 1993 47 183. 941866 J. Geochem. Explor. 1993 47 251. 941893 Appl. Zeeman Graphite Furn. At. Absorpt. Spectrom. Chem. Lab. Toxicol. 1992 179. 941894 Nippon Kagaku Kaishi 1993,4 395.941895 Nippon Kankyo Eisei Senta Shoho 1992,19 60.941896 Nippon Kaisui Gakkaishi 1992 46 370. 941897 Nippon Kankyo Eisei Senta Shoho 1992,19 35. 941901 Nucl. Instrum. Methods Phys. Res. Sect. B 1993 B75 262. 941902 Nucl. Instrum. Methods Phys. Res. Sect. B 1993 B75 415. 941904 Nucl. Instrum. Methods Phys. Res. Sect. B 1993 B77 203. 941923 Rocz. Glebozn. 1992 43 51. 941925 Sb. Vys.Sk. Zemed. Praze Fak. Agron. Rada A 1992,54,91.94/926 Sb. Vys. Sk. Zemed. Praze Fak. Agron. Rada A 1992 54 99. 941928 Sci. Total Environ. 1993 133 153. 941940 Trans. Inst. Min. Metall. Sect. B 1992 101 B9. 941944 Water Air Soil Pollut. 1993 66 145. 941946 Xibei Daxue Xuebao Ziran Kexueban 1992 22 191. 941949 Yongu Pogoso Hanguk Chawon Yonguso 1992 KR-91-3D 61. 941971 Appl. Opt. 1993 32 4890. 941979 Spectrochim. Acta Part B 1993,48 1291.941981 Spectrochim. Acta Part B 1993 48 1303. 941984 Ann. Clin. Biochem. 1993 30 142. 941986 Anal. Chim. Acta 1993,278 125. 941991 Appl. Spectrosc. 1993 47 330. 941996 Fresenius’ J. Anal. Chem. 1993 345 512. 94/1001 Spectrochim. Acta Part B 1993 48 553. 94/1010 Spectrochim. Acta Part B 1993 48 723. 9411011 Talanta 1993 40 669.9411021 Anal. Lett. 1993 26 1227. 9411024 Anal. Sci. 1993,9,415.94/1025 Anal. Sci. 1993,9,423.94/1028 Appl. Zeeman Graphite Furn. At. Absorpt. Spectrom. Chem. Lab. Toxicol. 1992 227. 9411030 Bull. Chem. SOC. Jpn.,. 1993 66,1404.9411033 Chem. Anal. (Warsaw) 1992,37,641.94/1040 Chem. Listy 1992 86 563. 9411042 Chem. Listy 1992 86 617. 9411044 Chem. Listy 1992 86 692. 9411067 Guangpuxue Yu Guangpu Fenxi 1992 12 81. 9411078 ICP Inf. Newsl. 1993 18,473. 94/1080 Indian J. Environ. Prot. 1992 12 581.9411084 J. Chin. Chem. SOC. (Taipei) 1993 40 241. 9411088 J. Indian Chem. SOC. 1992,69,699.94/1089 J. Korean Chem. SOC. 1993 37 327. 9411091 J. Radioanal. Nucl. Chem. 1993 170 171. 46 R Journal of Analytical Atomic Spectrometry February 1995 Vol. 109411092 J. Radioanal.Nucl. Chem. 1993 170 259. 9411094 Lab. Equip. Dig. 1993 31 31. 9411097 Lihua Jianyan Huaxue Fence 1993 29 104. 9411104 Microchem. J. 1992 46 30. 9411117 Nippon Kagaku Kaishi 1993 5 561. 9411118 Nippon Kagaku Kaishi 1993 6 715. 9411130 Spectra 2000 [Deux Mille] 1993 170 40. 9411151 Wutan Yu Huatan 1992 16 304.9411152 Yankuang Ceshi 1992,11,217.94/1153 Yankuang Ceshi 1992 11 221. 9411154 Yankuang Ceshi 1992 11 236. 9411155 Yankuang Ceshi 1992 11 249. 9411156 Yankuang Ceshi 1992 11 252. 9411157 Yankuang Ceshi 1992 11 260. 9411161 Yankuang Ceshi 1992 11 348. 9411162 Yankuang Ceshi 1992,11,357.94/1165 Zavod. Lab. 1992,58,23.94/1177 Can. J. Appl. Spectrosc. 1993 38 103. 9411182 Spectrochim. Acta Part B 1993 48 1365. 9411184 Spectrochim. Acta Part B 1993 48 1381. 9411186 Spectrochim.Acta Part B 1993 48 1411. 9411194 Bunseki Kagaku 1993 42 423 9411199 Zh. Anal. Khim. 1993 48 166. 9411200 Zh. Anal. Khim. 1993 48 526.9411206 Chemosphere 1993,26,2055.94/1213 Guangpuxue Yu Guangpu Fenxi 1992 12 83. 9411215 Guangpuxue Yu Guangpu Fenxi 1992,12,95.94/1216 Guangpuxue Yu Guangpu Fenxi 1992 12 111. 9411223 Guangpuxue Yu Guangpu Fenxi 1993 13 127. 9411224 Guangpuxue Yu Guangpu Fenxi 1993 13 131. 9411236 Guangpu Shiyanshi 1993 10 21. 9411237 Guangpu Shiyanshi 1993 10 25. 9411247 LaborPraxis 1993 17 46. 9411258 Yejin Fenxi 1993 13 49. 9411260 Yejin Fenxi 1993 13 53. 9411261 Yejin Fenxi 1993 13 11. 9411276 Anal. Chem. 1993 65 585A. 9411281 Anal. Chem. 1993 65 2468. 9411283 Anal. Chem. 1993 65 2485. 9411322 Talanta 1993 40 975. 9411345 Appl.Surf. Sci. 1993 70 63. 9411356 Can. Mineral. 1992,30 1023. 9411357 Can. Mineral. 1992,30 1049. 9411358 Can. Mineral. 1993 31 1. 9411359 Can. Mineral. 1993 31 19. 9411363 Chem. Geol. 1993 106 229. 9411364 Chem. Geol. 1993 106 251. 9411373 Dokl. Akad. Nauk 1993 329,342.9411381 Geochem. J. 1992,26,105.94/1382 Geostand. Newsl. 1993 17 81. 9411383 Gig. Sanit. 1992 7 19. 9411386 Geochim. Cosmochim. Acta 1993 57 1339. 9411387 Geochim. Cosmochim. Acta 1993,57,3479.94/1390 Haiyang Yu Huzhao 1992 23 550. 9411423 Kankyo Kagaku 1993 3 476. 9411424 Kyushu Daigaku Chuo Bunseki Senta Hokoku 1992,lO. 9411442 Nucl. Instrum. Methods Phys. Res. Sect. B 1993 B73 403. 9411485 Sci. Total Environ. 1993 130 275. 9411486 Shigen to Kankyo 1993 2 331. 9411489 Spectroscopy (Eugene Oreg.) 1993 8 32.9411502 Turang Tongbao 1993 24 87. 9411535 Second. Ion Mass Spectrom. SIMS 8 Proc. Int. Conf. 8th 1991 517. 9411542 Second. Ion Mass Spectrom. SIMS 8 Proc. Int. Conf. 8th 1991 685.9411543 Second. Ion Mass Spectrom. SIMS 8 Proc. Int. Con$ 8th 1991 689. 9411561 Fresenius’ J. Anal. Chem. 1993,346 162.9411563 X-ray Spectrom. 1993 22 244. 9411569 X-ray Spectrom. 1993 22 220. 9411572 X - ray Spectrom. 1993 22 248. 9411574 X-ray Spectrom. 1993 22 260. 9411578 X-ray Spectrom. 1993 22 281. 9411586 X - ray Spectrom. 1993 22 328. 9411587 X-ray Spectrom. 1993 22 332. 9411590 Appl. Radiat. Isot. 1993 44 1101. 9411601 Quim. Anal. 1993 12 57. 9411602 Zh. Anal. Khim. 1992 47 629.9411604 Anal. Chem. 1993,65,2510.94/1605 Anal. Chem. 1993 65 2590. 9411611 Anal. Chim. Acta 1993 279 241.9411614 Anal. Chim. Acta 1993,279,273. 9411615 Anal. Chim. Acta 1993 281 135. 9411616 Anal. Chim. Acta 1993,281 185. 9411623 Fenxi Huaxue 1993 21 662. 9411624 Fenxi Huaxue 1993 21 740. 9411626 Fenxi Huaxue 1993 21 761. 9411640 Fresenius’ J. Anal. Chem. 1993 346 643. 9411643 Fresenius’ J. Anal. Chem. 1993 346 689. 9411648 Talanta 1993 40 791. 9411650 Talanta 1993 40 1077. 9411656 Acta Univ. Palacki. Olomuc. Fac. Rerum Nut. 1991 104 157. 9411664 An. Asoc. Quim. Argent. 1993 81 57. 9411692 Arab Gulf J. Sci. Res. 1993 11 47. 9411693 Asian J. Chem. 1993 5 743. 9411698 Biomass Bioenergy 1993 4 103. 9411717 Bull. Korean Chem. SOC. 1993 14 330. 9411723 Chem. Geol. 1993 107 133. 9411726 Chikyu Kagaku (Nippon Chikyu Kagakkai) 1992,26 17. 9411731 Collect. Czech.Chem. Commun. 1993 58 1013. 94/1732 Comm. Eur. Communities [Rep.] EUR 1993 EUR 14763 86 pp. 9411733 DECHEMA Biotechnol. Conf. 1992 5 913. 9411734 Dhaka Univ. Stud. Part B 1993 41 133. 9411736 Earth Planet. Sci. Lett. 1993 117,431. 9411737 Earth Sci. Rev. 1992 32 235. 9411744 Environ. Int. 1993 19 285. 9411745 Environ. Monit. Assess. 1993 25 87. 9411756 Fuel 1993 72 1227. 9411758 Food Struct. 1993 12 67 9411762 Gen. Tech. Rep. NC (North Cent. For. Exp. Stn.) 1992 150 57. 9411763 Geochem. J. 1992 26 395. 9411764 Geochim. Bras. 1990 4 119.9411765 Geofis. Int. 1992,31,289.94/1766 Ghana J. Chem. 1993 1 338. 9411775 Guangpuxue Yu Guangpu Fenxi 1992 12(5) 63. 9411782 Guilin Yejin Dizhi Xueyuan Xuebao 1991 11,437. 9411783 Health Phys. 1993 65 147. 9411785 Huanjing Baohu (Taipei) 1992 15 29.9411786 Huanjing Baohu (Taipei) 1992 15 64. 9411787 Huanjing Kexue 1993 14 82. 9411790 Huaxue Tongbao 1993 5 43. 9411793 IARC Sci. Publ. 1992 118 287. 9411796 Indian J. Environ. Prot. 1993 13 20. 9411797 Inst. Phys. Conf. Ser. 1992 128 205. 9411801 Inter-nish 92 Int. Congr. Surf. Finish. 1992 3 1513. 9411805 J. Anal. Appl. Pyrolysis 1993 25 37. 9411812 J. Chromatogr. 1993 644 153. 9411815 J Food Saf. 1992 13 7. 9411816 J. Great Lakes Res. 1993 19 175. 9411828 Kankyo Kagaku 1993 3 400. 9411831 Kenkyu Hokoku-Himeji Kogyo Daigaku Kogakubu 1992 45 80. 9411833 Khim. Tekhnol. Vody 1993 15,255.9411845 Mar. Chem. 1993,42,223.94/1854 Mikrochim. Acta 1993 110 167. 9411855 Mikrochim. Acta 1993 110 217. 9411857 Mokuzai Gakkaishi 1993 39 48. 9411861 Nahrung 1992 36 451.9412071 Mikrochim. Acta 1993 112( 1-4) 19. 9412099 Pertanika 1992 15 171. 9412102 Pint. Acabados I d . 1993 35 53. 94/2103 Plants Biomonit. 1993 395. 9412127 Sci. Agric. (Piracicaba Braz.) 1993 50 121. 94/2128 Sci. Total Environ. 1993,133,285.9412131 Shigen Kankyo Taisaku 1993 29 651. 9412133 Shokuhin Eiseigaku Zasshi 1993 34 148. 9412145 Umweltwiss. Schadst.-Forsch. 1993 5 130. 9412146 Verre (Paris) 1992 6 277. 9412150 Vom. Wasser 1993 80 245. 9412158 WLB. Wasser Luft Boden 1993 37 64. 9412170 Zhongguo Dizhi Kexueyuan Yichang Dizhi Kuangchan Yanjiuso Sokan 1992,18,201.94/2174 Zhongguo Zhoagyao Zazhi 1993 18 223. 9412184 J. Anal. At. Spectrom. 1993 8 989. 9412191 J. Anal. At. Spectrom. 1993 8 1029. 9412194 J. Anal. At. Spectrom. 1993 8 1053. 9412195 J.Anal. At. Spectrom. 1993 8 1059.9412196 J. Anal. At. Spectrom. 1993,8 1067.9412198 J. Anal. At. Spectrom. 1993 8 1085. 9412199 J. Anal. At. Spectrom. 1993 8 1091. 9412200 J. Anal. At. Spectrom. 1993 8 1097. 9412210 J. Anal. At. Spectrom. 1994 9 7. 9412219 Spectrochim. Acta Part B 1993 48 217.9412223 Chem. Geol. 1993 106 187. 9412224 Chem. Geol. 1993 106 219. 9412225 Chem. Geol. 1993 106 467. 9412226 Chem. Geol. 1993 107 97. 9412227 Chem. Geol. 1993 109 1. 9412228 Chem. Geol. 1993,109,125.94/2229 Geostand. Newsl. 1993,17,209.94/2230 Geostand. Newsl. 1993 17 127 9412231 Geostand. Newsl. 1993,17,223. 9412232 Geostand. Newsl. 1993 17,217.9412233 Geochim. Cosmochim. Acta 1993 57 4513. 9412234 Geochim. Cosmochim. Acta 1993,57,4947.94/2235 Geochim. Cosmochim. Acta 1993,57,4119.94/2236 Geochim.Cosmochim. Acta 1993 57 1625. 9412237 Geochim. Cosmochim. Acta 1993 57 2907. 9412256 Analyst (London) 1993 118 1007. 9412261 Fenxi Huaxue 1993 21 704. 9412268 X-Ray Spectrom. 1993 22 125. 9412279 Zh. Anal. Khim. 1993 48 898. 9412280 Analusis 1993 21 249. 9412281 Fenxi Ceshi Xuebao 1993 12 64. 9412290 Henliang Fenxi 1993 9 48. 9412291 Int. J. Environ. Anal. Chem. 1993 50 9. 9412292 Int. Lab. 1993 23 14 16. 9412297 Lihua Jianyan Huaxue Fence 1993 29 159. 9412298 Lihua Jianyan Huaxue Fence 1993 29 179. 9412299 Microchem. J. 1993 48 184. 9412309 Aerosol Sci. Technol. 1992 17 213. 9412346 At. Spectrosc. 1993 14 144. 9412347 At. Spectrosc. 1993 14 148. 9412349 At. Spectrosc. 1993 14 152.9412352 Fresenius’ J. Anal. Chem. 1992,342 299.9412353 Fresenius’ J.Anal. Chem. 1992 342 306. 9412357 X-ray Spectrom. 1993 22 132. 9412374 Magmatic Processes and Plate Tectonics Geol. SOC. Spec. Publ. (London) 76 1993 501. 9412386 Can. J. Appl. Spectrosc. 1993 38 131. 9412387 Can. J. Appl. Spectrosc. 1993 38 145.9412389 Chem. Papers 1993 47 225. 9412390 Collect. Czech. Chem. Commun. 1993 58 Journal of Analytical Atomic Spectrometry February 1995 Vol. 10 47 R2905. 9412403 J. Anal. At. Spectrom. 1994 9 25R. 9412415 J. Radioanal. Nucl. Chem. 1993,167,237.9412416 J. Radioanal. Nucl. Chem. 1993 167 283. 9412417 Report 1991 EPA/600/3-91/065; Order No. PB92-106939 77 pp. 9412418 J. Radioanal. Nucl. Chem. 1993,167,295. 9412428 Adv. X-Ray Anal. 1992 35B 965. 9412446 Nucl. Instrum. Methods Phys. Res. Sect B 1992 68 115. 9412452 Prepr. Pap.-Am. Chem. SOC. Div. Fuel Chem. 1993 38 279. 9412453 Atmos. Enuiron. Part B 1992 26 505. 9412454 Adv. X-Ray Anal. 1992 35B 959.9412474 Ont. Geol. Surv. Misc. Pap. 1992,16,164.94/2475 Adu. X-Ray Anal. 1992 35B 755. 9412483 Geochim. Cosmochim. Acta. 1992 56 4059. 9412497 Indian J. Environ. Prot. 1992 12 445. 9412527 Nucl. Instrum. Methods Phys. Rex Sect. B 1993 75 576. 9412537 Anal. Chim. Acta 1993 282 63. 9412538 Anal. Chim. Acta 1993 282 437. 9412546 Anal. Proc. (London) 1993 30 442. 9412552 Anal. Sci. 1993 9 843. 9412555 Analyst (London) 1993 118 1107. 9412564 Bunseki Kagaku 1993 42 T135. 9412572 Fresenius’ J. Anal. Chem. 1993 345 53. 94/2580 Fresenius’ J. Anal. Chem. 1993 346 1058. 9412585 Fresenius’ J. Anal. Chem. 1993 347 238. 9412586 Fresenius’ J. Anal. Chem. 1993 347 256. 9412588 Fresenius’ J. Anal. Chem. 1993 347 324. 9412592 Talanta 1993,40 1477.9412597 Analusis 1993,21 293. 9412604 British Standard BS 7020 Section 8.2 1993 (IS0 4688-1 1990) 15 Oct 1993 pp. 16. 9412605 British Standard BS 7020:Part 15 1993 (IS0 10203 1993) 15 Oct 1993 pp. 16.9412607 Can. Mineral. 1993 31 371. 9412609 Chishitsu Nyusu 1992 450 16. 9412610 Chishitsu Nyusu 1992 450 42. 9412634 Geostand. Newsl. 1993 17(1) 5. 9412640 Henliang Fenxi 1993 9 99. 9412642 Int. J. Environ. Anal. Chem. 1993 50 193. 9412643 Int. J. Enuiron. Anal. Chem. 1993 51 223. 9412644 Int. J. Environ. Anal. Chem. 1993 52 215. 9412665 Inst. Phys. Con$ Ser. 1992 128 217. 9412691 J. Geol. SOC. China 1993 36 203. 9412692 J. Geophys. Rex [Atmos.] 1993 98 10,595. 9412695 J. Radioanal. Nucl. Chem. 1993,171,425.9412697 J. Radioanal. Nucl. Chem. 1993,172 117.9412698 J. Radioanal. Nucl. Chem. 1993,173,313.9412707 Kankyo Kagaku 1993,3,390.94/2710 Lihua Jianyan Huaxue Fence 1993 29 265. 9412715 Lihua Jianyan Huaxue Fence 1993 29 291. 9412730 Mikrochim. Acta 1993 111 207. 9412734 Nucl. Instrum. Methods Phys. Res. Sect. B 1993 83 275. 9412738 Pap.-Geol. Surv. Can. 1992,91-2 187. 9412743 Radiocarbon 1992,745. 9412750 Sci. Total Environ. 1993 135 131.9412792 Sep. Sci. Technol. 1994 29 781. 9412793 Spec. Pub1.-R. SOC. Chem. 1993 124 (Applications of Plasma Source Spectrometry 11) 1. 9412794 Spec. Pub1.-R. SOC. Chem. 1993 124 (Applications of Plasma Source Spectrometry 11) 108. 9412805 Zavod. Lab. 1993 59(8) 22. 9412806 Zavod. Lab. 1993 59(8) 27. 9412807 Zhongguo Dizhi Kexueyuan Yichang Dizhi Kuangchan Yanjiuso Sokan 1991,17 153.9412810 Anal. Chim. Acta 1993,283,261. 9412811 Anal. Chim. Acta 1993,284 181. 9412812 Anal. Chim. Acta 1993 284 327. 9412816 Appl. hot. Radiat. Conserv. Environ. Proc. Int. Symp. 1992 17. 9412824 Fenxi Ceshi Xuebao 1993,12(5) 97. 9412825 Fenxi Shiyanshi 1993,12( l) 103. 9412830 Inst. Phys. Con$ Ser. 1992 128 209. 9412835 Isotopenpraxis 1992 28 106. 9412849 Soil Sci. SOC. Am. J. 1993 57 410. 9412850 Soil Sci. SOC. Am. J. 1993 57 981. 9412851 Spec. Pub1.-R. SOC. Chem. 1993 124(Applications of Plasma Source Mass Spectrometry 11) 29. 9412852 Spec. Pub1.- R. SOC. Chem. l993,124(Applications of Plasma Source Mass Spectrometry 11) 48. 9412853 Spec. Pub1.-R. SOC. Chem. 1993 124(Applications of Plasma Source Mass Spectrometry 11) 83. 9412854 Spec. Pub1.- R. SOC. Chem. 1993 124(Applications o f Plasma Source Mass Spectrometry 11) 115. 94/2865 Yankuang Ceshi 1993 12 161. 9412869 Prib. Tekh. Eksp. 1993 (2) 244. 9412889 Lihua Jianyan Huaxue Fence 1994 30( l) 15. 9412891 Fenxi Shiyanshi 1994 13(2) 20. 9412906 J. Anal. At. Spectrom. 1994 9 187. 9412913 J. Anal. At. Spectrom. 1994 9 223. 9412914 J. Anal. At. Spectrom. 1994 9 227. 9412915 J. Anal. At. Spectrom. 1994 9 231. 9412917 J. Anal. At. Spectrom. 1994 9 241. 9412923 J. Anal. At. Spectrom. 1994 9 273. 9412925 J. Anal. At. Spectrom. 1994 9 285. 9412926 J. Anal. At. Spectrom. 1994 9 291. 9412929 J. Anal. At. Spectrom. 1994 9 307. 9412931 J. Anal. At. Spectrom. 1994 9 315. 9412934 J. Anal. At. Spectrom. 1994 9 337. 9412956 J. Anal. At. Spectrom. 1994 9 469. 9412957 J. Anal. At. Spectrom. 1994 9 477. 9412958 J. Anal. At. Spectrom. 1994 9 483. 9412962 J. Anal. At. Spectrom. 1994 9 519. 9412966 J. Anal. At. Spectrom. 1994 9 543. 9412967 J Anal. At. Spectrom. 1994 9 547. 9412982 J. Anal. At. Spectrom. 1994 9 663. 48 R Journal of Analytical Atomic Spectrometry February 1995 Vol. 10

ISSN:0267-9477    

DOI:10.1039/JA995100009R

出版商:RSC    

年代:1995

数据来源: RSC

摘要:

Federation of Analytical Chemistry and Spectroscopic Societies (FACSS) XXI St. Louis MO USA The 1994 FACSS meeting held in St. Louis was my first experience of a North American conference. As such I was totally unprepared for the size of the meeting; 113 separate sessions containing nearly 900 oral presentations and all to be completed in only 44 days! It is surely a testament to the work of the FACSS committee and organizers that such a large conference ran as smoothly as this one did. With such a large number of sessions the conference is able to cover a wide range of topics. Although the traditional analytical spectroscopic techniques (atomic molecular and mass) provided the greater parts of this years programme sessions covering electrochemistry separation science and bioanalytical clinical and pharmaceutical sciences also contributed significantly to the agenda.I was personally pleased to see that a number of chemometrics sessions were offered in the programme. These sessions including a session of practical tutorials offered a glimpse into the power that mathematics and statistics have to offer the analytical chemist in both academia and industry. In all of the sessions I attended the session chairs did an excellent job in keeping to the schedule. This is essential if people are to be able to move between lectures in parallel The Conference Hall 2-7 October 1994 sessions which is only natural at a conference the size of FACSS. often as many as 13 offered the conference a wide choice of lectures at any given time. This choice is I believe both the strength and weakness of such a large meeting.Often throughout the week I found myself wanting to be in two or even three places at the same time. This is obviously a very healthy situation for any conference. Unfortunately though the natural consequence of this choice is that a number of what can perhaps be called non-mainstream (in the context of the conference) sessions were poorly attended. This is unfortunate because a number of excellent talks were given with only small audiences in attendance. There will always be certain people who draw large audiences. These people are after all the cornerstone of any successful conference. However it can be disheartening for any speaker to present their work at a major conference like FACSS and only receive a small audience.One session that did not suffer from a small audience was the GF-AAS session dedicated to the memory of Professor Klaus Dittrich who passed away last year. The speakers invited by session organizer Debbie Bradshaw had The large number of parallel sessions Journal of Analytical Atomic Spectrometry collaborated with or were friends of Professor Dittrich. The presentations covered many aspects of AAS including the application of hydride generation techniques the reduction of chloride interferences solids analysis and instrumentation. Denton presented a comparison of charge-injection device (CID) and charge-coupled device (CCD) technology. Although the paper appeared in the first ‘Recent Advances in Raman Spectroscopy’ session it was general enough to be of interest to any spectroscopist wishing to keep abreast of this rapidly advancing field.R. E. Russo and A. J. Fernandez in two separate papers described the use of an ICP to study the fundamental principles involved in the laser ablation of solid samples. Good correlation was found between the laser power density and the ICP signal intensity. However due to the poor reproducibility of the ablation process the technique provided poor precision for analytical use. Cynthia Mahon described some preliminary work completed on a field deployable instrument for the analysis of bulk solids. The instrument based upon a dc-arc with a CID-based spectrograph is designed to give a complete sample fingerprint in the field and thus minimize the time between sample collection and preliminary analysis.Direct sample injection as a high efficiency method of sample introduction for ICP-AES and ICP-MS was described by Eric Salin where improvements in detection limits of up to 500 were reported. Lisa Wright discussed the use of non-invasive spectroscopic techniques to monitor the conditions of an ICP for diagnostic purposes. This is likely to be an increasingly important topic as instrument manufacturers strive to design evermore intelligent instrumentation. In a chemometrics session Stephen Morgan described how mathematics and statistics can be used to help the analyst to optimize the design of an experiment and to interpret the data correctly. This lecture clearly demonstrated the advantages that can be gained by employing experimental optimization procedures at an early stage in the design of any experiment.The ICP Atomic Emission session on Early on the first morning M. Bonner Journal of Analytical Atomic Spectrometry February 1995 Vol. 10 15 NDaran Sadler The Exhibitors’ Hall Delegates enjoying the gala evening Wednesday afternoon included two presentations both from instrument manufacturers describing axial viewing of an ICP. This is currently the ‘hot’ topic in ICP-AES at least amongst instrument manufacturers. Both papers described improvements to detection limits that can be gained from mounting the torch horizontally and viewing the plasma along its axis rather than through its radius. The degree of improvement could not be agreed upon and seems to be dependant upon instrumentation plasma operating conditions and sample composition.There is clearly much more work to be done in this area. The exhibitors’ hall. which was also used for the poster presentations had stands from over 50 companies. Several manufacturers used th.e conference to launch new instruments or products of which the multi-element ET-AAS instrument from Perkin-Elmer attracted a great deal of interest. The two poster sessions on Tuesday and Wednesday were reasonably well attended although it was a pity that the posters were not available for viewing until late in the afternoon. The Wednesday afternoon poster session did not seem as well attended as the Tuesday session possibly because delegates had returned to their hotels to prepare for the Gala later in the evening.The Gala evening held in the St. Louis Zoo Living World Center was a great success. The delegates had the chance to explore the Living World Center a mix of live animals and interactive displays prior to dinner. A 25 minute film ‘A World Alive’ then followed. After the film the presentation of awards was made; the FACSS Distinguished Service Award was presented to Mr. L. Felix Schneider and to Dr. F. Monte Evans. The Hirschfeld Awards went to Jeanette K. Rice and W. Russell Everret whilst Diana S. West was awarded the FACSS Student Award. At the end of the conference I was left with the feeling that it had been a week well spent. The lectures had on the whole been informative and lively whilst discussions with delegates working in similar fields were always thought provoking often stimulating and certainly never dull. I shall look forward to the next FACSS meeting in Cincinnati. DARAN SADLER Department of Strathclyde Glasgow G1 l X L UK 16 N Journal of Analytical Atomic Spectrometry February 1995 Vol. 10

ISSN:0267-9477    

DOI:10.1039/JA995100015N

出版商:RSC    

年代:1995

数据来源: RSC

摘要:

BOOK REVIEWS Flame Spectrometry In Environment Analysis A Practical Guide Malcolm S. Cresser. Pp. x + 108. Royal Society of Chemistry (London Cam- bridge). g29.50. ISBN 0 85186 734 0. This book is intended for environmental scientists who in the authors own words have ‘neither the time nor the desire to be able to learn enough to answer trivial pursuit type questions on theory or history of atomic spectroscopy. They wish instead to be able to obtain rapidly safely inexpensively and with minimal mental effort analytical results of sufficient accuracy to meet a specific purpose.’ A description that would appeal to my students I thought not just lazy environmental scientists. However after examination I decided that non- environmental scientists with no background in AAS would also find this book helpful for the determination of samples.This monograph is divided into nine chapters. Chapter one gives a very basic background to the absorption of light by atoms and the difference between atomic and molecular absorption. The history of the technique and early important discoveries are included which assist the reader’s understanding. Chapter two covers the instrument and the essential components required for element determinations. The various means by which the sample is transported to the atomizer and the importance of this is well presented. Some humour is interjected here when over efficient extraction systems are described and a poor sparrow has its flight path altered as a consequence. Other very useful material is dealt with in Chapter three on the various interferences encountered when using AAS.Throughout the author compares AAS with flame emission and atomic fluorescence which helps the reader to make decisions on the technique to use for their particular samples and the elements to be determined. Chapter four provides a good section on instrument optimization which is very helpful as most text books never mention the very important parameters which need to be adjusted in order to obtain good results. Chapter five is the key section describing how to prepare samples for analysis. Samples which are not treated correctly prior to analysis are not worth determining as the results will be in error. The seventh chapter gives guidance to the beginner on elements which can be analysed and helpful hints on how to do the analysis for a series of commonly encountered elements.In summary the final two chapters cover quality control and safety which are both very important. I liked this book as throughout the author uses analogies which make the material readable and easy to understand. Although various accessories are described which would enable one to measure low levels of elements ICP and graphite furnace are not included as they are beyond the scope of the book. It nevertheless is a practical book for anyone starting to use flame AAS. It is packed with good advice and information to help the analyst obtain reliable results and reflects the authors vast experience in AAS. A very useful book for undergraduates doing Environmental Chemistry courses or postgraduate students doing one year MSc degree courses in Analytical Chemistry.DAVID JAMES ROBERTS School of Chemistry University of Bristol Cantocks Close Bristol BS8 1TS Environmental Sampling for Trace Analysis Edited by Bernd Markert. Pp. xxx + 524. VCH (Weisheim). DM 248. ISBN 3 527 30051 1. Over the past ten years the field of Analytical Chemistry has undergone extensive development with regard to separation and detection systems and also the chemometric treatment of data thus providing adequate methodologies to carry out the simultaneous determination of several components of a same sample at very low concentrations. However during this time little attention has been paid to important aspects in some cases considered until now as minor points like sampling storage and sample pretreatment and because of that the Achilles’ heel of todays analytical chemists is these aspects.So a book on environmental sampling is very welcome. The book edited by Markert provides some basic principles and a series of practical examples in order to take representative environmental samples and to avoid their contamination or loss of trace components. The text contains twenty-seven chapters written by specialists from several countries particularly from Germany Hungary and USA but also including some studies developed in China Bulgaria Estonia etc. All these studies are organized in four sections concerning ( i ) historical aspects ( i i ) general aspects of environmental sampling and trace analysis ( i i i ) some examples of sampling air water soils and sediments and plants and animals and (iv) a literature survey including references about sampling and related topics and a list of the norms about sampling from the International Organization of Standardization in Geneva.The book covers general statistical aspects related to the representation of samples and specific topics like problems related to the results below the detection limits. However the consideration of general aspects only represents twenty percent of the book the main part being devoted to examples of sampling of various types of environmental materials. In this section the chapters concerning soils and sediments are by far the most interesting and better organized those devoted to water analysis are excessively repetitive and badly coordinated.However this section includes an interesting chapter by U. M. Cowgill which contains some references to sampling problems related to determinations in ice snow rain dew and fog and also includes a good study by H. Klapper et al. which treats aspects concerning the cost of sample collection. The section concerning air sampling is well organized and includes a very good chapter by Zielinska and Fujita about the sampling of organic gases. The section concerning plants and ani- mals contains an excellent chapter by Maavara et al. about the sampling of wood red ants but suprisingly does not contain any studies on the sampling of fish or molluscs. Chapters concerning the sampling of plants are very complete and contain some topics like that of stemflow and throughfall rain precipitation in forests which contribute to evidence on the complexity of sampling in environmental analysis. Some of the studies included in the examples for sampling section are related to specific studies on the River Elbe or the Taiwan sediment pollution by wastewaters. Unfortunately there is a lack of homogeneity throughout the text for example different chapters use different citation systems for references and not all the authors have followed the 1990 IUPAC recommendations for sampling. In addition some topics of current importance in analysis like in field sampling and speciation are not considered in the text. The book will be of interest to analytical chemists involved in environmental analysis and will enable them to improve their practices by carefully considering the sampling process. MIGUEL D E LA GUARDIA Department of Analytical Chemistry University of Valencia 46100 Buriassot. SDain Journal of Analytical Atomic Spectrometry February 1995 VoE. 10 17 N

ISSN:0267-9477    

DOI:10.1039/JA995100017N

出版商:RSC    

年代:1995

数据来源: RSC

摘要:

DIARY OF CONFERENCES AND COURSES 1995 Pittcon '95 The Pittsburgh Conference on Analytical Chemistry and Applied Spectroscopy March 5-10 New Orleans Louisiana USA Details can be found in J. Anal. At. Spectrom. 1994,9,49N. For further information contact The Pittsburgh Conference 300 Penn Center Boulevard Suite 332 Pittsburgh PA 15235-5503 USA. Telephone (412) 825-3220; toll free (800) 825-3221; fax (412) 825-3224. Short Course. Gas Liquid Chroma tograph y March 20-24 Loughborough UK The aim of the course is to present a rapid but comprehensive introduction to the theory and practice of modern gas- liquid chromatography for the comparative newcomer to the technique or those more experienced analysts moving into the area. The lecture course will include the following topics an introduction to the background theory of practical chromatography; origins of modern chromatography; instrumentation; general and selective detectors; columns and liquid phases including capillary columns and injection techniques; derivatisation for GLC; specialized sample preparation methods; applications in qualitative and quantitative analysis; ancillary techniques including GC-MS; problems in practical chromatography and instrumentation; use of integrators. Practical sessions will play a major role in the programme.Experiments will be available to give participants a detailed knowledge of the fundamental principles operation and uses of modern instrumentation. For further details contact Mrs. S. J. Maddison Department of Chemistry University of Technology Loughborough Leics.LEll 3TU. Telephone (01509) 222575,222563; Fax (01509) 233163. 3rd SAS - Symposium on Analytical Sciences March 28-30 Paris France The 3rd Symposium on Analytical Sciences will be held from March 28 to 30 1995 at the Parc des Expositions Porte de Versailles Paris simultaneously with the Salon du La boratoire. The division of Analytical Chemistry of SociCtC Franqaise de Chimie is sponsoring the 3rd SAS. Technological advances in the following areas will be covered Sample pretreatment; Atomic Spectrometry; Industrial & Instrumental Applications of Chemometrics; Separation Sciences; Molecular Spectroscopy and Electroanalysis and Bio Sensors. For further information contact The Scientific Committee -. 3rd SAS 7 rue d'Argout 75002 Paris France.Telephone (33.1)42.33.47.66. Fourth International Conference on Progress in Analytical Chemistry in the Steel and Metals Industry May 16-18 Jean Monnet Building Luxembourg Details can be found in J. Anal. At. Spectrom. 1994,9 50N. For details of providing a contribution to the programme or other information contact CEC/CETAS Conference R. Jowitt British Steel plc Technical Teesside Laboratories PO Box 11 Grangetown Middles brough Cleveland TS6 6UB. Telephone + 44 642 467144; Fax + 44 642 460321. 43rd ASMS conference on Mass Spectrometry and Allied Topics May 21-25 Atlanta GA USA For further details contact ASMS 1201 Don Diego Avenue Smta Fe NM 87501 USA. Telephone 505 989 4517; Fax 505 989 1073. 5th Annual Flow Injection Atomic Spectroscopy Short Course June 6-8 Amherst Massachusetts USA Details can be found in J.Anal. At. Spectrom. 1994,9,68N. For further information contact Julian F. Tyson Department of Chemistry Lederle GRC Tower University of Massachusetts Box 34510 Amherst MA 01003-4510 USA. Telephone (413) 545 0195; Fax (413) 545 4846. Short Course. High-Performance Liquid Chromatography July 3-7 Loughborough UK The course consists of lectures practical excercises and discussion sessions. These enable the comparative beginner or those with a little knowledge of HPLC to meet experienced chromatographers from industrial and other laboratories and from the instrument manufacturers in both formal and informal surrondings. Lectures will be given by Loughborough University staff and by visiting lecturers from industrial and other laboratories and from the instrument firms.Topics include introductory theory; columns and stationary phases; forms of HPLC; basic instrumention; detectors; method development and solvent selection; integrators; detector systems; pharmaceutical and other applications; problem solving in practical chromatography. For further details contact Mrs. S. J. Maddison Department of Chemistry University of Technology Loughborough Leics. LEll 3TU. Telephone (01509) 222575,222563; Fax (01509) 233163 SAC 95 July 9-15 Hull UK Details can be found in J. Anal. At. Spectrom. 1995,10,13N For further information contact The Secretary Analytical Division The Royal Society of Chemistry Burlington House Piccadilly London W1V OBN UK. Vth COMTOX Symposium on Toxicology and Clinical Chemistry of Metals July 10-13 University of British Columbia Vancouver British Columbia Canada Details can be found in J.Anal. At. Spectrom. 1994,9,26N. The Third Asian Conference on Analytical Sciences ASIANALYSIS 111 August 20-24 Seoul Korea The Third Asian Conference on Analytical Sciences (ASIANALYSIS 111) will be held in Seoul Korea on August 20-24,1995. The conference is to provide a forum for scientists in Asia to discuss their scientific research and exchange their mutual interest on a broad area of analytical chemistry for the regional cooperation. It consists of invited lectures contributed talks poster presentations a special workshop for graduate students and scientific exhibition. Topics covered will include Atomic Spectroscopy; Molecular Spectrometry; 18 N Journal of Analytical Atomic Spectrometry February 1995 Vol.10Chromatography and Separation Science; Electroanalytical Chemistry; Surface Analysis; Chemometrics; Environmental Analysis; Bioanalytical Chemistry and Teaching and Education in Analytical Chemistry. For further details contact Prof. Hasuck Kim (Secretariat) ASIANALYIS 111 Department of Chemistry College of Natural Sciences Seoul National University Seoul 151-742 Korea. Telephone + 82(2)880-6638; Fax + 82(2)889-1568; E-mail hausukim@KRSNUCC 1 .BITNET 13th Australian Symposium on Analytical Chemistry. In conjunction with 4th Environment Chemistry Conference - Chemistry in Tropical and Temperate Environments 9-14 July Darwin Northern Territory Australia The scientific program will incorporate plenary sessions invited speakers oral and poster presentations and workshops.There will be three concurrent sessions - two will focus on analytical chemistry and a third on environmental chemistry. Plenary sessions will include Professor Ramon Barnes University of Massachusetts USA “ICP-MS an indispensable tool for modern biological and environmental chemistry analysis”; Professor Milton Lee Brigham Young University USA “Utilization of open tubular and packed capillary columns in micro column separations”; Professor Joseph Wang New Mexico State University USA “Electrochemical stripping procedures for on-site monitoring of trace metals”; Professor Malcolm Cresser University of Aberdeen UK “Pollution effects research in soils and water quality”; Professor Ulrich Forstner Technical University Hamburg Germany “Environmental chemistry of solid waste”; and Professor Francois Morel Massachusetts Ins ti tu te of Technology USA “Aquatic chemistry”.Analytical Chemistry topics covered will include Atomic spectroscopy; Capillary eletrophoresis; Chemometrics; Electrochemistry; Flow injection analysis; FT-IR; Forensic chemistry; Food chemistry; GC-MS; HPLC and ion chromatography; ICP-MS; Pesticide residue chemistry; Quality assurance in analytical chemistry and Supercritical fluid chromatography. Other specialist mini-symposia and workshops including exhibitors sessions will be held. For further information contact Dr. Brian Salter-Duke Secretary 13AC/4EC Organizing Committee RACI GPO Box 363 Darwin NT 0801 Australia.Colloquium Spectroscopicum Internationale (CSI) XXIX August 27-September 1 Leipzig Germany Details can be found in J . Anal. At. Spectrom. 1993,8,50N. Colloquium Spectroscopicum Internationale (CSI) XXIX Post Symposium ICP-MS September 1-4 Wernigerode/Hartz Germany Details can be found in J. Anal. At. Spectrom. 1994,9,46N. Euroanalysis IX September 1-7 Bologna Italy Details can be found in J. Anal. At. Spectrom. 1995,10 14N. Further information is available from Professor Luigia Sabbatini Euroanalysis IX Dipartimento di Chimica Universita di Bari Via Orabona 4,70126 Bari Italy. 8th International Conference on Coal Science September 10- 15 Instituto Nacional del Carbon CSIC Apartado 73 33080 Oviedo Spain Details can be found in J. Anal. At. Spectrom. 1994,9,61N.For further details contact Dr. Juan M. D. Tascon 8th ICCS Scientific Programme Chairman Instituto Nacional del Carbon CSIC Apartado 73,33080 Oviedo Spain. Telephone + 34.8.528.08.00; Fax + 34.8.529.76.62. Federation of Analytical Chemistry and Spectroscopy Societies Conference October 15-20 Cincinnati Ohio USA The conference traditionally brings together a full range of analytical disciplines and this year especially so. You will find a comprehensive technical programme state-of-the-art instruments display and a variety of helpful professional services including an employment clearing house and numerous workshops. The symposia will include the following topics Electrochemistry; Clinical/Pharmaceutical Analyses; Separation Sciences; Atomic Spectroscopy; Surface Science and Materials; Environmental Analytical Chemistry; Sensors and Molecular Spectroscopy.Presentations will be in the form of poster sessions and talks. Talks will be both invited and submitted with invited lectures given by the top internationally recognized members of their fields. Papers should discuss original and previously unpublished work. Titles should be submitted by March 31 1995. Two-hundred fifty word abstracts must be recieved by June 30 1995 and authors will be informed within about one month of thier acceptance and the presentation format. Papers will be presented in the symposia open sessions and poster sessions. The talks will be typically 20 or 40 minutes and open discussion is encouraged. For further information contact Joseph A. Caruso FACSS National Office 198 Thomas Johnson Dr.Suite S-2 Frederick MD 21702 USA. Telephone (301) 694-8122; Fax (301) 694-6860. Sixth Surrey Conference on Plasma Source Spectrometry September 17-20 Jersey UK The Surrey Conference now an established biennial event in the international spectroscopy calendar will be held this year in the resort town of St. Helier on Jersey in the Channel Islands. concerned with the inorganic analysis of materials by plasma source spectrometry. Scientific sessions are planned on instrumentation and theory sample introduction techniques analysis of solid samples and application of ICP-MS to biological industrial geological and environmental samples. A new venture this year will be a session dedicated to all aspects of plasma spectrometry in the Earth Sciences covering both ICP-AES and ICP-MS analysis.of invited lectures contributed papers posters and a discussion workshop. Social events will include an informal reception on Sunday and conference dinner on Tuesday evening. Invited speakers include Dr. Nick Walsh (Royal Holloway) Dr. Conrad Gregoire (Geological Survey Canada) Prof. Ray Barnes (Univ. of Machussettes) and Dr. Alan Gray (Imperial College). are invited on topics associated with all aspects of plasma source mass spectrometry and on ICP-AES and ICP-MS studies in the Earth Sciences. Abstracts are required by July 28th 1995 and abstract forms will be sent on receipt of the attached application form. Authors are encouraged to submit manuscripts at the conference for publication subject to the normal review procedure in a special issue of the Journal of Analytical Atomic Spectrometry. For further details contact Dr.K. Jarvis NERC ICP-MS Facility Centre for The conference will be mainly The scientific programme will consist Papers (oral and poster presentations) Journal of Analytical Atomic Spectrometry February 1995 Vol. 10 19NAnalytical Res. in the Environment (CARE) Imperial College at Silwood Park Buckhurst Road Ascot Berkshire SL5 7TE UK. Telephone +44(0) 344 294517; Fax +44(0) 344 873997. International Symposium on Environmental Biomonitoring and Specimen Banking December 17-22 Honolulu Hawaii USA Details can be found in J. Anal. At. Spectrom. 1994,9,59N. For further information contact K. S. Subramanian Environmental Health Directorate Health Canada Tunney’s Pasture Ottawa Ontario K1A OL2 Canada (phone 6 13-957- 1874; fax 613-941-4545) or G.V. Iyengar Center for Analytical Chemistry Room 235 B 125 National Institute of Standards and Technology Gaithersburg MD 20899 USA (Telephone 301-975-6284; Fax 301-921-9847) or M. Morita Division of Chemistry and Physics National Institute for Environmental Studies Japan Environmental Agency Yatabe-Machi Tsukuba Ibaraki 305 Japan (Telephone 81-298-51-61 11 ext. 260; Fax 8 1-298-56-4678). First Mediterranean Basin Conference on Analytical Chemistry November 5-10 Cordoba Spain The ‘Grupo Espectroquimico’ of the Spanish Royal Societies of Chemistry and Physics invite your participation in the First Mediterranean Basin Conference on Analytical Chemistry to be held in Cordoba Spain in November 1995.The aims of the conference are to promote collaboration among analytical scientists of the different interested countries to promote new opportunities for young scientists in the Mediterranean Sea area and to stimulate the progress of Analytical Chemistry as a whole by solving analytical problems affecting the Mediterranean Basin. Topics covered will include Education of Analytical Chemistry; Environmental Analytical Chemistry; Agriculture and Food ,4nalysis; Geoanalytical Chemistry and Benefitiation of Minerals; Biomedical Analysis; Archeometry and Art Objects Preservation and Quality Assurance and Harmonization of Procedures. For further details contact Prof. Alfred0 Sanz-Medel Department of Physical and Analytical Chemistry Faculty of Chemistry.University of Oviedo C/ Julian Claveria no 8. 3006 Oviedo (Spain). Telephone 34/’85/ 103474-103485; Fax 34/85/103480. Biological Applications of Inorganic Mass Spectrometry November 8-9 Norwich U K A two day meeting November 8-9 1995 at the Institute of Food Research Norwich (accommodation at the University of East Anglia) sponsored by the British Mass Spectrometry Society and the Atomic Spectroscopy Group Royal Society of Chemistry. Ledingham (Glasgow University) on Resonance ionization; Helen Crews (CSL Norwich) on Speciation by ICP-MS; Barry Sharp (Loughborough University) on New sample introduction techniques in biological applications of ICP-MS; Sue Fairweat her-Tait IFR Norwich) giving a biologists/nutritionists perspective; Mike James (Sellafield) on Plutonium uptake in biological systems; Peter Sadler (Birkbeck College) on Metabolism of drugs and metalloprotcins; Ann Waddilove (Loughborough University) on Laser microprobe mass spectrometry and other speakers on multi-element analysis electrospray ICP-MS and radionuclides to be confirmed.For further informatioin contact Dr. Fred Mellon Institute of Food Research Norwich Laboratory Norwich Research Park Colney Norwich NR4 7UA UK. Telephone + 44(0) 1603 255 299 (direct line) + 44 (0) 1603 255 000 (switchboard/paging); Fax + 44 (0) 1603 fred.mellon@BBSRC.AC.UK. Presenters will include Ken 452578 +44 (0)1603 507723; E-MAIL European Workshop in Chemometrics September 17-22 Bristol U K The University of Bristol will hold its annual 1995 European Workshop in Chemometrics in Bristol 17-22 September 1995.For further details contact Mrs. C. Hutcheon School of Chemistry University of Bristol Contock’s Close Bristol BS8 LTS UK. Telephone +44(0)117-928 7645 ext. 4221; Fax + 444 0) 1 17-925 1295 1996 1996 Winter Conference on Plasma Spectrochemistry January 8-13 Fort Lauderdale Florida USA Details can be found in J. Anal. At. Spectrom. 1994,9,53N. For further information contact Dr. R. Barnes ICP Information Newsletter Department of Chemistry Lederle GRC Towers University of Massachusetts Box 34510 Amherst MA 01003-4510 USA. Telephone (413) 545 2294; Telefax (413) 545 4490. International Schools and Conferences on X-Ray Analytical Methods January 18-25 Sydney Australia Details can be found in J. Anal. At. Spectrom. 1994,9,47N. For further information contact AXAA ’96 Secretariat GPO Box 128 Sydney NSW 2001 Australia. Telephone 6 1 2 262 2277; Fax 6 1 2 262 2323; Telex AA 176511 TRHOST. Analytica Conference 96 April 23-26 Munich Germany Details can be found in J. Anal. At. Spectrom. 1994,2,69N. For further information contact Messe Miinchen GmbH Messegelande D-80325 Munchen Germany. Telephone +49 89 51 07-0; Telex 5 212 086 ameg d; Fax + 49 89 5 1 07- 177. 20N Journal of Analytical Atomic Spectrometry February 1995 Vol. 10

ISSN:0267-9477    

DOI:10.1039/JA995100018N

出版商:RSC    

年代:1995

数据来源: RSC

摘要:

FUTURE ISSUES WILL INCLUDE- On-line Preconcentration of CrIII and Speciation of Chromium in Waters by Flame Atomic Absorption Spectrometry-Benyamin Pascullean Christine M. Davidson and David Littlejohn Field Sampling Technique for the ‘Fast Reactive’ Aluminium Fraction in Waters Using a Flow Injection Mini-column System with Inductively Coupled Plasma Atomic Emission Spectrometric and Inductively Coupled Plasma Mass Spectrometric De tec tion-Ben Fairman Alfredo Sanz-Medel and Phil Jones Knowledge-based Coniputer System for the Detection of Matrix Interferences in Atomic Absorption Spectrometric Methods-W. Penninckx P. Vankeerberghen D. L. Massart and J. Smeyers-Verbeke Inductively Coupled Plasma in Fluorescence Spectrometry Source and Atom/Ion Reservior. Invited Lecture- Stanley Greenfield 20N Journal of Analytical Atomic Spectrometry February 1995 Vol.10Comparison of Chemical Modifiers for the Determination of Gold in Biological Fluids by Electrothermal Atomic Absorption Spectrome try-Nikolaos S. Thomaidis Efrosini Piperaki and Constantinos E. Efstathiou Automated Technique for Mercury Determination at Sub-nanogram Per Litre Level in Natural Waters-Daniel Cossa Jane Sanjuan Jacques Cloud Peter B. Stockwell and Warren T. Corns Isotope Ratio Measurements in Strontium Using Two-Photon Two- Colour Resonance Ionization Mass Spectrometry-Indral K. Perera Ian C. Lyon and Grenville Turner Determination and Speciation of Heavy Metals in Sediments from the Cumbrian Coast NW England UK-Abd Ulhafid Belazi Christine M. Davidson Gillian E. Keating David Littlejohn and Martin McCartney Automatic Wavelength Cali brat ion Procedure for use with an Optical Spectrometer and Array Detector- Daran A. Sadler David Littlejohn and Charles V.Perkins Effect of Elevated Gas Pressure on Atomization in Graphite Furnace Continuum Source Atomic Absorption Spectrometry with Linear Photodiode- Array Detection-C. M. M. Smith and J. M. Harnly Effect of Furnace Atomization Temperatures on Simultaneous Multielement Atomic Absorption Measurements Using a Transversely- Heated Graphite Atomizer-James M. Harnly and Bernard Radziuk Analytical Minimalism Applied to the Determination of Trace Elements by Atomic Spectrometry-D. J. Halls Simultaneous Measurement of Isotope Ratios in Solids by Laser Ablation with a Twin Quadrupole Inductively Coupled Plasma Mass Spectrometer-L.A. Allen H.-M. Pang A. R. Warren and R. S. Houk Determination of Selenium in Human Hair and Nail by Electrothermal Atomic Absorption Spectrometery-I. Harrison David Littlejohn and G. S. Fell Speciation of Arsenic by the Determination of Total Arsenic and Arsenic (111) in Marine Sediment Samples by Electrothermal Atomic Absorption Spectrometry-Pilar Bermejo-Barrera M. C. Barciela-Alonso M. Ferron-Novais and A. Bermejo- Barrera Optimal Accuracy Precision and Sensitivity of Inductively Coupled Plasma Optical Emission Spectrometry Examples with the Bioanalysis of Aluminium-Trevor Burden J. J. Powell P. D. Taylor and R. P. H. Thompson Studies on Solvent Extraction to Determine Iodide Indirectly by Electrothermal Atomic Absorption Spectrometry-Pilar Bermejo-Barrera M.Aboal-Somoza A. Moreda-Pineiro and A. Bermejo-Barrera COPIES OF CITED ARTICLES The Royal Society of Chemistry Library can usually supply copies of cited articles. For further details contact The Library Royal Society of Chemistry Burlington House Piccadilly London WlV OBN UK. Tel +44 (0) 71-437 8565; fax +44 (0) 71-287 9798; Telecom Gold 84; BUR210; Electronic Mailbox (Internet) LIBRARY@RSC.ORG. If the material is not available from the Society’s Library the staff will be pleased to advise on its availability from other sources. Please note that copies are not available from the RSC at Thomas Graham House Cambridge. Journal of Analytical Atomic Spectrometry February 1995 Vol. 10 21 NComparison of Chemical Modifiers for the Determination of Gold in Biological Fluids by Electrothermal Atomic Absorption Spectrome try-Nikolaos S.Thomaidis Efrosini Piperaki and Constantinos E. Efstathiou Automated Technique for Mercury Determination at Sub-nanogram Per Litre Level in Natural Waters-Daniel Cossa Jane Sanjuan Jacques Cloud Peter B. Stockwell and Warren T. Corns Isotope Ratio Measurements in Strontium Using Two-Photon Two- Colour Resonance Ionization Mass Spectrometry-Indral K. Perera Ian C. Lyon and Grenville Turner Determination and Speciation of Heavy Metals in Sediments from the Cumbrian Coast NW England UK-Abd Ulhafid Belazi Christine M. Davidson Gillian E. Keating David Littlejohn and Martin McCartney Automatic Wavelength Cali brat ion Procedure for use with an Optical Spectrometer and Array Detector- Daran A.Sadler David Littlejohn and Charles V. Perkins Effect of Elevated Gas Pressure on Atomization in Graphite Furnace Continuum Source Atomic Absorption Spectrometry with Linear Photodiode- Array Detection-C. M. M. Smith and J. M. Harnly Effect of Furnace Atomization Temperatures on Simultaneous Multielement Atomic Absorption Measurements Using a Transversely- Heated Graphite Atomizer-James M. Harnly and Bernard Radziuk Analytical Minimalism Applied to the Determination of Trace Elements by Atomic Spectrometry-D. J. Halls Simultaneous Measurement of Isotope Ratios in Solids by Laser Ablation with a Twin Quadrupole Inductively Coupled Plasma Mass Spectrometer-L. A. Allen H.-M. Pang A. R. Warren and R. S. Houk Determination of Selenium in Human Hair and Nail by Electrothermal Atomic Absorption Spectrometery-I.Harrison David Littlejohn and G. S. Fell Speciation of Arsenic by the Determination of Total Arsenic and Arsenic (111) in Marine Sediment Samples by Electrothermal Atomic Absorption Spectrometry-Pilar Bermejo-Barrera M. C. Barciela-Alonso M. Ferron-Novais and A. Bermejo- Barrera Optimal Accuracy Precision and Sensitivity of Inductively Coupled Plasma Optical Emission Spectrometry Examples with the Bioanalysis of Aluminium-Trevor Burden J. J. Powell P. D. Taylor and R. P. H. Thompson Studies on Solvent Extraction to Determine Iodide Indirectly by Electrothermal Atomic Absorption Spectrometry-Pilar Bermejo-Barrera M. Aboal-Somoza A. Moreda-Pineiro and A. Bermejo-Barrera COPIES OF CITED ARTICLES The Royal Society of Chemistry Library can usually supply copies of cited articles. For further details contact The Library Royal Society of Chemistry Burlington House Piccadilly London WlV OBN UK. Tel +44 (0) 71-437 8565; fax +44 (0) 71-287 9798; Telecom Gold 84; BUR210; Electronic Mailbox (Internet) LIBRARY@RSC.ORG. If the material is not available from the Society’s Library the staff will be pleased to advise on its availability from other sources. Please note that copies are not available from the RSC at Thomas Graham House Cambridge. Journal of Analytical Atomic Spectrometry February 1995 Vol. 10 21 N

ISSN:0267-9477    

DOI:10.1039/JA995100020N

出版商:RSC    

年代:1995

数据来源: RSC

摘要:

ATOMIC SPECTROMETRY UPDATED REFERENCES The address given in a reference is that of the first named author and is not necessarily the same for any co-author. 951183. 951184. 951185. 9511 86. 951187. 95/188. 951189. 951190. 951191. 951192. 951193. 951194. 951195. Robinson J. W. Atomic absorption a view of the early days Anal. Chem. 1994 66 472A. (Louisiana State Univ. Baton Rouge LA 70803-1804 USA). Jackson K. W. Mahmood T. M. Atomic Absorption Atomic Emission and Flame Emission Spectrometry Anal. Chem. 1994 66 252R. (Wadsworth Center Lab. Res. New York State Dept. Health Albany NY Beauchemin D. Yves Le Blanc J. C. Peters G. R. Persaud A. T. Plasma Emission Spectrometry Anal. Chem. 1994 66 462R. (Dept. Chem. Queen's Univ. Kingston ON Canada K7L 3N6). Boumans P. W. J. M. Detection limits and spectral interferences in atomic emission spectrometry Anal. Chem.1994 66 459A. (Philips Res. Labs. Eindhoven Netherlands). Arruda M. A. Z. Zagatto E. A. G. Maniasso N. Kinetic determination of cobalt and nickel by flow injection spectrophotometry Anal. Chim. Acta 1993 283 476. (Cent. Energia Nucl. Agric. Univ. Sao Paulo P.O. Box 96 13400 Piracicaba Brazil). Do Nascimento D. B. Schwedt G. Off-line and on-line preconcentration of trace levels of beryllium using complexing agents with atomic spectrometric and fluorometric detection Anal. Chim. Acta 1993 283 909. (Inst. Anorg. Anal. Chem. Tech. Univ. Clausthal Paul-Ernst-Str. 4 38678 Clausthal-Zellerfeld Germany). Wagatsuma K. Hirokawa K. Assessment of the population of neutral and singly ionized zinc species in argon and argon-nitrogen inductively coupled plasma by atomic absorption spectrometry Anal.Chim. Acta 1993 284 351. (Inst. Mater. Res. Tohoku Univ. Katahira 2-2-1 Sendai Japan 980). Volynsky A. B. Tikhomirov S. V. Senin V. G. Kashin A. N. Some processes occurring in graphite furnaces used for electrothermal atomic absorption spectrometry in the presence of organic chemical modifiers Anal. Chim. Acta 1993 284 367. (Lab. Org. Anal. Dept. Chem. Moscow State Univ. 119899 Moscow Russia). Le X.-c. Cullen W. R. Reimer K. J. Effect of cysteine on the speciation of arsenic by using hydride generation atomic absorption spectrometry Anal. Chim. Acta 1994 285 277. (Dept. Chem. Univ. British Columbia Vancouver Canada). Trojanowicz M. Pyrzynska K. Flow-injection precon- centration of Co" on l-nitroso-2-naphthol-3,6- disulfonate-modified alumina for flame atomic absorp- tion spectrometry Anal.Chim. Acta 1994 287 247. (Dept. Chem. Univ. Warsaw Pasteura 1 02-093 Warsaw Poland). Laserna J. J. Calvo N. Cabalin L. M. Imaging and space-resolved spectroscopy in the Xe-Cl laser ablation of noble metals with charge-coupled device detection Anal. Chim. Acta 1994 289 113. (Dept. Anal. Chem. Fac. Sci. Univ. Malaga Malaga Spain E-2907 1). Dadfarnia S. Green I. McLeod C. W. On-line preconcentration and determination of lead by fibrous alumina and flow injection atomic absorption spec- trometry Anal. Proc. 1994 31 61. (Sch. Sci. Sheffield Hallam Univ. Sheffield UK S1 1WB). Kagawa K. Tani M. Ueda H. Sasaki M. Mizukami K. TEA carbon dioxide laser-induced plasma with a plane shock wave structure Appl.12201-0509 USA). 951196. 951197. 951198. 9.51199. 951200. 951201. 951202. 951203. 951204. 951205. 951206. 951207. Spectrosc. 1993 47 1562. (Fac. Educ. Fukui Univ. Fukui Japan 910). Bye C. L. Scheeline A. Analyte matrix excitation investigations in the high-voltage spark discharge using an Cchelle-CCD system Appl. Spectrosc. 1993 47 2031. (Sch. Chem. Sci. Univ. Illinois Urbana IL 61801 USA). Linn J. H. Hanley K. J. Quantitative infrared spectroscopy of interstitial oxygen in silicon wafers using mulitvariate calibration Appl. Spectrosc. 1993 47 2102. (Anal. Serv. Harris Semicond. Melbourne FL 32901 USA). Thiem T. L. Salter R. H. Gardner J. A. Lee Y. I. Sneddon J. Quantitative simultaneous elemental deter- minations in alloys using laser-induced breakdown spectroscopy (LIBS) in an ultra-high vacuum Appl.Spectrosc. Spacecr. Interact. Branch Phillips Lab. Hanscom AFB MA 01731 USA). Cao J. Y. Narasaki H. Determination of selenium and antimony by hydride generation atomic absorption spectrometry using tetrahydroborate(II1) bound to an anion-exchange resin Bunseki Kagaku 1994 43 169. (Fac. Sci. Saitama Univ. Urawa Japan 338). Minamisawa H. Arai N. Okutani T. Preconcentration of copper(1r)-nitrosonaphthol- disulfonate complex on chitin and determination of copper by metal furnace AAS Bunseki Kagaku 1993 42 767. (Coll. Sci. Technol. Nihon Univ. Tokyo Japan 101). Luo X.-w. Qiu D. Chen Z.-j. Zhu S.-s. Study of mechanism of germane generation by using inductively coupled plasma atomic emission spectrometry Fenxi Huaxue 1993 21 1241.(Dept. Chem. Fudan Univ. Shanghai China 200433). Liu Q. Deng B. Atomization mechanism of elements on the graphite probe surface in the graphite furnace. VII. Atomization mechanism of germanium Fenxi Huaxue 1993 21 1258. (Dept. Appl. Chem. Taiyuan Univ. Technol. Taiyuan China 030024). Yu A.-m. Zhang H.:q. Jin Q.-h. Liu X.-j. Determination of gold silver platinum rhodium and palladium by low-powered microwave plasma torch atomic emission spectrometry using an ultrasonic nebulizer Fenxi Huaxue 1993 21 1320. (Dept. Chem. Jilin Univ. Changchun China 130023). Yang Y. Huang A.-m. Chen Y.-h. Program- controlled electrothermal evaporation dynamic molecu- lar absorption spectrophotometry Fenxi Huaxue 1994 22 156.(Antiepidem. Stat. Chengdu Chengdu China 6 1002 1 ) . Uebbing J. Ciocan A. Hiddemann L. Niemax K. Element analysis of solid samples by laser ablation and optical spectroscopy AIP Con$ Proc. 1993 288 109. (Inst. Spektrochem. Angew. Spektrosk. W-4600 Dortmund Germany). Vairavamurthy A. Manowitz B. Zhou W.-q. Jeon Y.-s. Determination of hydrogen sulfide oxidation products by sulfur K-edge X-ray absorption near-edge structure spectroscopy ACS Symp. Ser. 1994 550 412. (Dept. Appl. Sci. Brookhaven Natl. Univ. Upton NY 11973 USA). Puretzky A. A. Geohegan D. B. Haufler R. E. Hettich R. L. Zheng X. Y. Compton R. N. Laser ablation of graphite in different buffer gases AIP Con$ Journal of Analytical Atomic Spectrometry February 1995 Vol. 10 49 R951208. 951209.951210. 951211. 951212. 9512 1 3. 951214. 951215. 9512 16. 9512 17. 9512 18. 9 51219. 951220. 951221. 951222. 50R Proc. 1993 288 365. (Inst. Spectrosc. Troitsk Russia 142092). Gill R. J. AAS or ICP-OES Are they competing techniques? Am. Lab. (Shelton Conn.) 1993 25 24F 24H. (GBC Sci. Equip. Pty. Ltd. Dandenong 3175 Australia). Shijo Y. Yoshimoto. E. Sakurai S. Shimizu T. Kawamata Y. Determination of trace amounts of indium in high-purity aluminium by graphite furnace atomic absorption spectrometry after solvent extraction and micro-volume back-extraction Anal. Sci. 1994 10 277. Fac. Eng. Utsunomiya Univ. Utsunomiya Japan 321). Matsusaki K. Okada K. Oishi T. Sata T. Matrix modification with metal nitrates and organic com- pounds for the determination of germanium by graphite furnace atomic absorption spectrometry Anal.Sci. 1994 10 281. (Fac. Eng. Yamaguchi Univ. Ube Japan 755). Seo M. L. Lee S. S. Kim J. S. Park T. M. Determination of magnesium( 2 +) using 5-membered heterocyclic compound Anal. Sci. Technol. 1993 6 307. (Dept. Chem. Gyeongsang Natl. Univ. Chinju 660-701 South Korea). Buenzli J. C. G. Principle implementation and applications of Fourier-transform IR spectrometry Analusis 1993 21(5) M8 M11 M15. (Inst. Chim. Miner. Anal. Univ. Lausanne 1005 Lausanne Switzerland). Ouyang Y. Mansell R. S. Ou L. T. Method for measuring tetraethyl lead and total lead in organic solvents Bull. Environ. Contam. Toxicol. 1994 52 760. (Soil Water Sci. Dept. Univ. Florida Gainesville FL Biswas S. S. Patil P. B. Murty P. S. Emission spectroscopic determination of B and Cd in magnesium used in uranium production Bull.Mater. Sci. 1994 17 19. (Bhabha At. Res. Cent. Bombay 400 085 India). Dai K.-p. Determination of aluminium in zinc anode Cailiao Baohu 1993 26(5) 31. (Wuhan Mater. Prot. Inst. Wuhan China 430030). Pszonicki L. Essed A. M. Behaviour of the system lead-sodium-chloride ions-palladium during atomiz- ation in graphite furnace atomic absorption spec- trometry Chem. Anal. (Warsaw) 1993 38 759. (Inst. Nucl. Chem. Technol. Warsaw Poland) Ostrega P. Bulska E. Hulanicki A. Simultaneous determination of Cd and Pb by atomic absorption spectrometry with a tungsten-coil atomizer Chem. Anal. (Warsaw) 1993 38 779. (Dept. Chem. Univ. Warsaw Warsaw Poland). Wang Y. Yuan X.4 Zhang H.-q. Yang W.-j.Jin Q.-h. Study on analytical performance of low-powered ArMPT-AES Chin. Chem. Lett. 1993 4 917. (Dept. Chem. Jilin Univ. Changchun China 130023). Yun J. I. Sim U. C. An S. G. Determination of main elements by influence of tertiary components in flame photometric analysis Choson Minjujuui Znmin Konghwaguk Kwahagwon Tongbo 1993 (5) 34. (North Korea). Huang H.-p. Zhao Y.-x. Zheng J.-h. Lin S.4 Study of an on-line flow extraction system for flame atomic spectrometry and its application Diqiu Kexue 1993 18 810. (China Univ. Geosci. Wuhan China 430074). Martines L. J. An expert system and flow-through digestion device for the automation of sample prep- aration prior to inductively coupled plasma spectro- chemical analysis From Diss. Abstr. Int. B 1993 54( 2) 781. (Univ.Massachusetts Amherst MA USA). Azimi S. Lead in environmental samples Environ. Test. Anal. 1994 3( l) 54. (Lab. Serv. MBT Environ. Lab. Rancho Cordova CA USA). 3261 1-0290 USA). 951223. 951224. 9 5/22 5. 951226. 951227. 951228. 951229. 951230. 951231. 951232. 951233. 951234. 951235. 951236. 951237. Journal of Analytical Atomic Spectrometry February 1995 Vol. 10 Feng Z.-y. Li Y.-s. Xie F.-z. Direct determination of trace silver in geological samples by graphite furnace atomic absorption spectrometry Fenxi Ceshi Xuebao 1993 12(2) 57. (Changsha Res. Inst. Min. Metall. Changsha China). Lin Z.-x. Song J.-y. Mo S.-j. Background absorption of europium matrix in graphite furnace atomic absorp- tion spectrophotometry Fenxi Ceshi Xuebao 1993 12(4) 32. (Dept. Chem. South China Norm.Univ. Guangzhou China). Hou M.-y. Du Z.-h. Duan Y.-x. Liu J. Jin Q. Determination of manganese by microwave-induced plasma atomic absorption spectroscopy Fenxi Shiyanshi 1993 12(2) 64. (Dept. Chem. Jilin Univ. Changchun China 130023). Zhou Z.-h. Li H.-j. Xu J. Separation and preconcen- tration of trace silver with nitrocotton Fenxi Shiyanshi 1993 12(6) 65. (Dept. Chem. Eng. Guangdong Coll. Technol. Guangzhou China 5 10090). De Carlo E. Acquisition of a graphite furnace atomic absorption spectrometer Report 199 1 Order No. PB93-120822 5 pp. (Hawali Inst. Geophys. Honolulu HI USA). Grohse P. M. Luk K. K. Hodson L. L. Wilson B. M. Gutknecht W. F. Development of a field test method for the determination of lead in paint and paint-contaminated dust and soil Report 1993 EPA/600/A-93/064; Order No.PB93-173 128 23 pp. (Res. Triangle Inst. Research Triangle Park NC USA). Zhang LA Guo Y. Huang J.-f. Indirect determi- nation of trace chlorine by atomic absorption spec- trometry Guangpuxue Yu Guangpu Fenxi 1993 13( 2) 79. (Exp. Cent. Jiangxi Univ. Nanchang China 3 30047). Ma W.-y. A new analytical method-RIS-TOF (reson- ance ionization spectroscopy-time-of-flight) tech- nique Guangpuxue Yu Guangpu Fenxi 1993,13(2) 111. (Dept. Phys. Tsinghua Univ. 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Ecol. Port Orchard WA 98366-8204 USA). Oriol L. Alonso P. J. Martinez J. I. Pinol M. Serrano J. L. Structural studies of copper(I1)-chelated polymers derived from hydroxy-functionalized liquid crystalline homo- and copolyazomethines Macromolecules 1994 27 1869.(Inst. Ci. Mater. Aragon Univ. Zaragoza-Consejo Zaragoza Spain Tomera J. F. Lilford K. Harakal C. Vectorial analysis of hypertrophy calcium and cadmium depen- dence in normotensive and hypertensive rabbits Methods Find. Exp. Clin. Pharmacol. 1993 15 669. (Clin. Pharmacol. Lab. Shriners Burns Res. Cent. Cambridge MA USA). Giordano R. Ciaralli L. Gattorta G. Ciprotti M. Costantini S. Analysis of tricyclohexyltin hydroxide using Zeeman graphite furnace atomic absorption spectrometry Microchem. J. 1994 49 69. (Appl. Toxicol. Dept. 1st. Super. Sanita 00161 Rome Italy). Minami H. Zhang Q.-b. Itoh H. Atsuya I. Direct determination of chromium in biological materials by 50009). 951437.951438. 951439. 95/40. 951441. 951442. 951443. 951444. 9 51445. 951446. 951447. 95/448. 951449. 951450. Journal of Analytical Atomic Spectrometry February 1995 Vol. 10 solid-sampling atomic absorption spectrometry appli- cation of three-point estimation standard additions method Microchem. J. 1994 49 126. (Dept. Mater. Sci. Kitami Inst. Technol. Kitami Japan 090). Chiba M. Shinohara A. Inaba Y. Improved method for using atomic absorption spectrometry with a graphite furnace to determine tin in blood Microchem. J. 1994 49 275. (Sch. Med. Juntendo Univ. Tokyo Japan 113). Tsunoda K. Takano Y. Matsumoto K. Kawamoto H. Akaiwa H. Separation and concentration of the trimethylselenonium ion for its determination in urine by graphite furnace atomic absorption spectrometry Microchem.J. 1994 49 282. (Fac. Eng. Gunma Univ. Kiryu Japan 376). Nomizu T. Falchuk K. H. Vallee B. L. Zinc iron and copper contents of Xenopus laeuis oocytes and embryos Mol. Reprod. Deu. 1993 36(4) 419. (Cent. Biochem. Biophys. Sci. Med. Harvard Med. Sch. Boston MA 02115 USA). Matthews M. R. Parsons P. J. Carpenter D. O. Solubility of lead as lead(r1) chloride in HEPES-Ringer and artificial seawater (calcium-AS W) solutions Neurotoxicology 1993 14 283. (New York State Dept. Health Wadsworth Cent. Albany NY 12201-0509 USA). Suzuki K. Nakajima K. Otaki N. Kimura M. Kawaharada U. Uehara K. Hara F. Nakazato Y. Takatama M. Localization of metallothionein in aged human brain Puthol. Int. 1994 44 20. (Coll. Med. Care and Technol. Gunma Univ.Maebashi Japan 371). Iwamoto K. Tamura K. Azuma J. Determination of heavy metal elements in soils by inductively coupled plasma emission spectrometry Pedorojisuto 1992 36 95. (Fac. Agric. Kobe Univ. Kobe Japan). Bagshaw S. L. Cleland R. E. Is wall-bound calcium redistributed during the gravireaction of stems and coleoptiles? Plant Cell Enuiron. 1993 16 1081. (Bot. Dept. Univ. Washington Seattle WA 98195 USA). Van Steveninck R. F. M. Babare A. Fernando D. R. Van Steveninck M. E. Binding of zinc in root cells of crop plants by phytic acid Plant Soil 1993 155-156 525. (Sch. Agric. La Trobe Univ. Bundoora 3083 Australia). Lerner L. A. Kakhnovich Z. N. Epifanova L. M. Pb and Cd atomic absorption in graphite furnace by using soil suspensions Pochvouedenie 1993 (S) 118.(Pochven. Inst. im. V. V. Dokuchaeva Russia). Szteke B. Jedrzejczak R. Kos S. Aluminium content determination in food products of plant origin by the method of electrothermal atomic absorption spectro- photometry (ETAAS) Pr. Inst. Lab. Badaw. Przem. Spozyw. 1991 43 20. (Zakl. Anal. Zywn. Inst. Biotechnol. Przem. Rolno-Spozyw. Warsaw Poland) Jedrzejczak R. Determination of the content of arsenic lead copper zinc and tin in bottled fruit fruit pulp and jams by the methods of atomic absorption spectrometry (AAS) Pr. Inst. Lab. Badaw. Przem. Spozyw. 1991 43 31. (Zakl. Anal. Zywn. Inst. Biotechnol. Przem. Rolno-Spozyw. Warsaw Poland). Templeton D. M. Measurement of total nickel in body fluids. Electrothermal atomic absorption methods and sources of preanalytical variation Pure Appl.Chern. 1994,66 357. (Clin. Chem. Div. IUPAC Oxford UK). Sanchez J. Millan E. Use of ultrasound in digestion of biological reference materials for determination of heavy metals Quim. Anal. (Barcelona) 1992 11 3. (Dept. Quim. Appl. Univ. Pais Vasco San Scbastian Spain 20080). Pita Calvo C. Bermejo Barrera P. Bermejo Barrera A Use of magnesium nitrate as a matrix951451. 951452. 951453. 951454. 951455. 9 5/45. 951457. 9 514 5 8. 951459. 951460. modifier in direct determination of molybdenum in human serum by electrothermal atomization atomic absorption spectrometry Quim. Anal. (Barcelona) 1992 11 35. (Fac. Quim. Univ. Santiago de Compostela Spain). Araujo A. N. Lima J. L. F. C. Simultaneous determination of total calcium and sodium levels in blood serum using an FIA system with parallel detection by atomic absorption spectrophotometry and flame photometry Quim.Anal. (Barcelona) 1992 11 55. (Fac. Pharm. Univ. Oporto Oporto Portugal 4000). Salgado P. E. de Toledo Minoia C. Ronchi A. Gatti A. Levels of chromium in plasma and red blood cells after acute poisoning by potassium dichromate Rev. Cienc. Farm. (Sao Paulo) 1992 14 157. (Lab. Igi. Ind. Fondaz. Clin. Del Lavoro Pavia Italy). Minoia C. Sabbioni E. Ronchi A Gatti A. Pietra R. Nicolotti A. Fortaner S. Balducci C. Fonte A. Roggi C. Trace element reference values in tissues from inhabitants of the european community. IV. Influence of dietary factors Sci. Total Environ. 1994 141 181. (Lab. Igiene Ind. Fondazione Clin. Lavoro 27100 Pavia Italy).Piette M. Desmet B. Dams R. Determination of strontium in human whole blood by ICP-AES Sci. Total Enuiron. 1994 141 269. (Lab. Forensic Med. Univ. Gent B-9000 Ghent Belgium). Ansari T. M. Pervez H. Azam M. Quantitative analysis of trace elements in chewing tobacco brands of Pakistan by atomic absorption spectrometry Sci. Int. (Lahore) 1993 5 169. (Dept. Chem. Bahauddin Zakariya Univ. Multan Pakistan 60800). Kikuchi M. Mishima Y. Seki T. Problems of furnace atomic absorption spectrometry in fenbutatin oxide determination Sendai-shi Eisei Kenkyushoho 1992 (Pub. 1993) 22 226. (Sendai Munic. Inst. Public Health Sendai Japan 983). Zhou M.-j. Zhang M. Yan D.-f. Determination of lead in soil by slurry sampling graphite furnace atomic absorption spectrometry Shanghai Huanjing Kexue 1993 12( l) 31.(Fudan Univ. Shanghai China). Benhura M. A. N. Marume M. Viscosity behaviour of the mucilage extracted from Ruredzo (Dicerocaryum zanguebarium) StarchlStaerke 1994 46 106. (Dept. Biochem. Univ. Zimbabwe Harare Zimbabwe). Xiao G.-q. Tang R.-h. Wang S.-y. Cao T.-g. Li L.-y. Induction by ytterbium and europium of the synthesis of liver metallothionein in rabbit Shengwu Huaxue Zazhi 1994 10(1) 93. (Dept. Tech. Phys. Peking Univ. Beijing China 100871). Su Y.d. Bian Y.q. Gu S.-c. Ni Y.-m. Determination of trace cadmium [in soy sauce] by flame absorption 951461. 951462. 9 51463. 951464. 951465. 951466. 951467. 951468. 951469. spectrometry ( FAAS) after organic coprecipitation separation Tongji Daxue Xuebao 1992,20,213. (Dept. Chem. Tongji Univ.Shanghai China). Ross J. F. Broadwell R. D. Poston M. R. Lawhorn G. T. Highest brain bismuth levels and neuropathology are adjacent to fenestrated blood vessels in mouse brain after intraperitoneal dosing of bismuth subnitrate Toxicol. Appl. Pharmacol. 1994 124 191. (Hum. Environ. Saf. Div. Procter and Gamble Co. Cincinnati Aytekin C. Ensari N. Y. Kizil M. Kaya Z. Akkus M. Aydin G. Analysis of magnesium and some trace elements in urinary stone and hair by inductively coupled plasma atomic emission spectroscopy Turk. J. Med. Sci. 1993 19 277. (Fac. Art Sci. Univ. Dicle Diyarbakir Turkey). Rosiles Martinez R. Gonzalez Romero V. M. Lopez Lopez R. Pena Pina J. Comparative levels of selenium in hair of heifers from the Valley of Mexico suffering from sudden heart failure death and from healthy heifers at sea level Vet.Mex. 1993 24 135. (Fac. Med. Vet. Zootec. Univ. Nac. Auton Mexico Mexico City Mexico 04510). Shevchuk I. A. Lozinsky N. S. Makhno A. Ya. Extraction-atomic absorption determination of dithio- carbamate pesticides Ukr. Khim. Zh. (Russ. Ed.) 1993 59 863. (Donetsk Gos. Univ. Donetsk Ukraine). Chen SA. Zheng Y.-r. Qiu W. Xu L. Metallic prosthetic group of acid phosphatase from Branchiostoma belcheri (Gray) Xiamen Daxue Xuebao Ziran Kexueban 1992 31 682. (Dept. Biol. Xiamen Univ. Xiamen China). Huang Y. Zhang P. Li HA. Wu W.-g. Studies on trace element in hair of Rhinopithecus r roxellance Xibei Daxue Xuebao Ziran Kexueban 1993 23 442. (Res. Cent. Protect. Panda Wuoloan Natl. Protect. Region Wenchuan China 623006). Wang Y.-f. Liu WJ. Wang X.Zhou X.-z. A simple standard additions method for determination of lead in whole blood and reference value for children Zhongguo Yike Daxue Xuebao 1993 22 465. (2nd Affiliated Hosp. China Med. Univ. Shenyang China). Mertin D. Oravcova E. Sviatko P. Suvegova K. Determination of concentrations of some mineral substances in the organs of fox Zivocisna Vyroba 1993 38 979. (Vysk. Ustav Zivocisnej Vyroby Nitra Slovakia). Wu Q. Li Q.-f. Wang D.-y. Distribution and the content of selenium in carcinoma cells and its relation to glutathione peroxidase Xiamen Daxue Xuebao Ziran Kexueban 1993,32 204. (Lab. Cell Biol. Xiamen Univ. Xiamen China). OH 45239-8707 USA). Journal of Analytical Atomic Spectrometry February 1995 Vol. 10 59R

ISSN:0267-9477    

DOI:10.1039/JA995100049R

出版商:RSC    

年代:1995

数据来源: RSC

摘要:

Glossary of Abbreviations Whenever suitable elements may be referred to by their chemical symbols and compounds by their formulae. The following abbreviations are used extensively in the Atomic Spectrometry Updates. ac AA AAS AE AES A F AFS AOAC APDC ASV BCR CCP CMP CRM cv cw dc DCP DDC DMF DNA ECD EDL EDTA EDXRF EIE EPMA ETA ETAAS ETV EXAFS FAAS FAB FAES FAFS FANES FAPES FI FPD FT FTMS GC GD GDL GDMS Ge(Li) HCL hf HG HPGe HPLC IAEA IBMK ICP ICP-MS alternating current atomic absorption atomic absorption spectrometry atomic emission atomic emission spectrometry atomic fluorescence atomic fluorescence spectrometry Association of Official Analytical Chemists ammonium pyrrolidinedithiocarbamate anodic-stripping voltammetry Community Bureau of Reference capacitively coupled plasma capacitively coupled microwave plasma certified reference material cold vapour continuous wave direct current d.c.plasma dieth yldithiocarbamate N N-dimethylformamide deoxyribonucleic acid electron capture detection electrodeless discharge lamp ethylenediaminetetraacetic acid energy dispersive X-ray fluorescence easily ionizable element electron probe microanalysis electrothermal atomization electrothermal atomic absorption spectrometry electrothermal vaporization extended X-ray absorption fine structure flame AAS fast atom bombardment flame AES flame AFS furnace atomic non-thermal excitation spectrometry furnace atomization plasma excitation spectrometry flow injection flame photometric detector Fourier transform Fourier transform mass spectrometry gas chromatography glow discharge glow discharge lamp glow discharge mass spectrometry lithium-drifted germanium hollow cathode lamp high frequency hydride generation high-purity germanium high-performance liquid chromatography International Atomic Energy Agency isobutyl methyl ketone (4-methylpentan-2-one) inductively coupled plasma inductively coupled plasma mass spectrometry (ammonium pyrrolidin- 1-yl dithioformate) spectroscopy ID IR IUPAC LA LC LEAFS LEI LMMS LOD LTE MECA MIP MS NAA NaDDC NIES NIST NTA OES PIGE PIXE PMT PPm PTFE rf REE(s) RIMS RM RSD SEC SEM SFC Si ( Li) SIMAAC SIMS SR SRM SSMS STPF TCA TIMS TLC TMAH TOP0 TXRF uhf uv VDU vuv WDXRF XRF PPb QC SIB SIN isotope dilution infrared International Union of Pure and Applied Chemistry laser ablation liquid chromatography laser-excited atomic fluorescence spectrometry laser-enhanced ionization laser-microprobe mass spectrometry limit of detection local thermal equilibrium molecular emission cavity analysis microwave-induced plasma mass spectrometry neutron activation analysis sodium diethyldithiocarbamate National Institute for Environmental Studies National Institute of Standards and Technology nitrilo triace tic acid optical emission spectrometry particle-induced gamma-ray emission particle-induced X-ray emission photomultiplier tube parts per billion parts per million polytetrafluoroethylene quality control radiofrequency rare earth element(s) resonance ionization mass spectrometry reference material relative standard deviation signal to background ratio size-exclusion chromatography scanning electron microscopy supercritical fluid chromatography lithium-drifted silicon simultaneous multi-element analysis with a continuum source secondary ion mass spectrometry signal to noise ratio synchrotron radiation Standard Reference Material spark source mass spectrometry stabilized temperature platform furnace trichloroacetic acid thermal ionization mass spectrometry thin-layer chromatography tetramethylammonium hydroxide trioctylphosphine oxide total reflection X-ray fluorescence ultra-high frequency ultraviolet visual display unit vacuum ultraviolet wavelength dispersive X-ray fluorescence X-ray fluorescence 60 R Journal of Analytical Atomic Spectrometry February 1995 Vol.10

ISSN:0267-9477    

DOI:10.1039/JA995100060R

出版商:RSC    

年代:1995

数据来源: RSC

摘要:

Solid Sampling Electrothermal Vaporization Inductively Coupled Plasma Mass Spectrometry for the Determination of Arsenic in Standard Reference Materials of Plant Origin Published in Celebration of the 10th Anniversary FRANK VANHAECKE* SYLVIE BOONEN LUC MOENS AND RICHARD DAMS Laboratory of Analytical Chemistry Institute for Nuclear Sciences Ghent University Proeftuinstraat 86 B-9000 Ghent Belgium The direct determination of As in solid samples of plant origin using electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) is reported. The first phase of the work consisted of an optimization of the carrier gas flow rate and the heating cycle of the modified graphite furnace (ashing and vaporization temperatures). A systematic study of the signal profiles (signal intensity as a function of time) showed that As coming from the solid samples and As coming from liquid standards added to the solid material only showed an analogous behaviour on condition that these liquid spikes were previously dried before the solid sample was introduced into the sample boat.The potential of the technique was assessed by establishing figures of merit and analysing some standard reference materials for As. An absolute limit of detection of approximately 1 pg was established for As corresponding to a relative limit of detection of approximately 1 ng g-' for a typical sample mass of 1 mg. Results obtained for the As content in the samples analysed were not deteriorated by the presence of C1 as even on addition of amounts of C1 exceeding the C1 content of the samples no 40A85Cl+ interference on the 75A~+ signal could be established.For the determination of As in these reference materials of plant origin several methods of calibration were investigated including external calibration using both liquid and solid standards and single standard addition. The use of an internal standard (Sb) was studied and its requirement was assessed as being from advisable to imperative depending on the calibration method used. Although several methods offered possibilities for accurate determination (mean deviation between ETV-ICP-MS results and certified values < lo%) single standard addition was assessed to be the most practicable and straightforward method. Keywords Arsenic; electrothermal vaporization; inductively coupled plasma mass spectrometry; solid sampling; calibration methods Since its introduction inductively coupled plasma mass spec- trometry (ICP-MS) has aroused great interest and has become increasingly popular and widespread in the analytical com- munity.At present about one decade after its commercial introduction it has evolved into a well established technique for trace and ultra-trace element determination primarily owing to its extremely low limits of detection multi-element capabilities and the possibility of obtaining isotopic information on the elements determined. * Senior Research Assistant of the Belgian National Fund for Scientific Research. Journal of Analytical Atomic Spectrometry Originally ICP-MS was mainly intended for the analysis of aqueous samples and hence pneumatic nebulization is the most widespread and applied method for sample introduction.In spite of their low cost instrumental simplicity high sample throughput and good stability pneumatic nebulizers also show important drawbacks:' ( i ) a low transport efficiency (in combi- nation with a spray chamber typically 1-2%) (ii) the need for relatively large sample amounts (2 1 ml) (iii) the simultaneous introduction of analyte and matrix into the plasma giving rise to both spectral and non-spectral interferences and (iv) the limitation to liquid samples. As a result alternative sample introduction systems for ICP-MS are an important topic of current research. For the introduction of liquid samples into an ICP ultrasonic neb~lization,~?~ thermospray neb~lization,~ direct insertion nebulization,' monodisperse dried monopar- ticulate injection6 and electrothermal vaporization7-'* have already been used.Gaseous samples can be simply mixed with the carrier gas flow for injection into the central channel of the pla~ma.'~ For solid samples one can use an electric spark,20-22 laser a b l a t i ~ n ~ ~ - ~ ~ direct i n ~ e r t i o n ~ ' * ~ ~ - ~ ' and elec- trothermal v a p ~ r i z a t i o n ~ ~ - ~ ~ as a means of sample introduction into an ICP. For solutions electrothermal vaporization (ETV) shows several advantages over conventional pneumatic nebulization the most important being ( i ) the possibility of analysing small sample sizes (10 pl or less) (ii) higher transport efficiencies (20-80%) leading to lower limits of detection and (iii) the possibility of separating the analyte from the matrix using an appropriate temperature programme possibly in combination with the application of chemical modifiers leading to a signifi- cant decrease in both spectral (polyatomic ions containing atoms originating from the m a t r i ~ ) ~ ~ . ~ * and non-spectral (signal suppression or enhancement caused by the matrix) inter- ferences.Additionally ETV also offers the possibility of direct analysis of solid samples. Accurate and precise analysis of solid samples is of the utmost importance for materials that cannot or can only with difficulty be brought into solution. In general solid sampling analysis limits the necessary amount of often laborious and time-consuming sample pre-treatment leading to a reduced risk of contamination or analyte losses.Finally as samples are analysed without dilution lower limits of detection are also to be expected. Although the potential of ETV-ICP-MS for 'solid sampling' has been recognized for years only very few publications on the subject have appeared. Both Voellkopf et aL3' and Gregoire et aL4' reported on the analysis of solid samples using ETV-ICP-MS but both groups prefer to analyse slurries rather than (dry) solid samples. Wang et al? recently reported 'real' solid sampling ETV-ICP-MS. They explored the feasibility of this approach highlighted Journal of Analytical Atomic Spectrometry February 1995 Vol. 10 81some difficulties to be studied more intensively and concluded that in order to obtain accurate analysis results external calibration using a solid standard reference material (SRM) with a composition as similar as possible to that of the sample provides the best performance. In this paper we report on efforts made to combine the advantages of direct solid sampling with those of ICP-MS.In this first stage of solid sampling ETV-ICP-MS research arsenic was chosen to investigate the potential of the direct analysis of solids by ETV-ICP-MS because it is relatively volatile while biologically toxicologically and environmentally important. Arsenic was determined in a number of standard reference materials so that by comparing the results obtained with the certified values the accuracy could be evaluated. A discussion on the applicability of various methods of calibration (external calibration using both liquid and solid standards and single standard addition) and the need to use an internal standard is presented.Limitations or drawbacks of this approach were critically looked at and are also discussed. EXPERIMENTAL Instrumentation The ETV system used is a commercially available graphite furnace of the boat-in-tube type (SM-30 Grun Analytische Mess-Systeme Germany) originally designed for solid Sam- pling Zeeman-effect atomic absorption spectrometry (AAS). The modifications necessary to make it compatible for use with ICP atomic emission spectrometry (AES) and ICP-MS and a more detailed description of the device have been presented elsewhere.35 The furnace consists of a pyrolytic graphite-coated graphite tube into which slide sample boats of pyrolytic graphite-coated graphite (which can be easily and reproducibly loaded with the aid of a pair of tweezers) placed on a rail which is rigidly mounted in front of the furnace.During the heating cycle one end of the furnace is closed using a shutter kept in position by a catch-spring. During operation an argon gas flow the flow rate of which is controlled by a mass flow controller (Model 5876 Brooks Instruments The Netherlands) is swept through the furnace such that during the vaporization stage ‘sample particles’ are dispersed in the carrier gas and hence transported into the central channel of the ICP. Only when loading sample boats into the furnace an additional argon flow in the opposite direction to the carrier gas flow was used in order to prevent air from entering the furnace and subsequently the plasma.During the heating cycle no so-called secondary transport gas (coolant gas)13,38,42 was used. The heating cycle of the furnace was controlled by an in-house developed computer program and the temperature could be monitored using an optical pyrometer (PY20 Grun Optik Germany). The ETV system was coupled via 60 cm x 10 mm i.d. silicone- rubber tubing to a Perkin-Elmer Sciex Elan 5000 ICP mass spectrometer. Silicone-rubber has the advantage of being stretchable such that the transfer tube is straight and analyte losses by impact on the tubing walls are reduced to a minimum. A three-way valve was used to vent vapours generated during the drying ashing and cleaning steps.As a result only vapours generated during the vaporization step of the heating pro- gramme were allowed to reach the plasma so that contami- nation (torch interface lens stack interface pump oil) and plasma overloading risks could be reduced to a minimum. Instrumental Parameters Operation conditions tures) and the carrier gas flow rate. Results of this optimization are presented under Results and Discussion. For the radiofre- quency (r.f.) power the default setting of 1000 W was used while the lens settings were optimized using pneumatic nebuliz- ation as a means of sample introduction and did not require any further tuning when switching to electrothermal vaporiz- ation. Further operation conditions are summarized in Table 1. Measurement parameters Measurements were made using the quantitative analysis mode.For transient signals lasting only a few seconds while monitor- ing two or more nuclides it is important to hop fast enough between the nuclides concerned in order to obtain a representa- tive image of the corresponding signal profiles. On the other hand if the dwell times are chosen too small the duty cycle (the ratio of actual measuring time to quadrupole mass spec- trometer settling time) decreases so that the total measurement time is used less effi~iently.~~ These considerations led to the measurement parameters also summarized in Table 1. The three-way valve was switched manually to the ‘measuring position’ 12 s before the start of the vaporization stage while the measurement itself was started 2 s before the beginning of the vaporization stage.Samples and Standards In order to evaluate the potential of ETV-ICP-MS for the determination of As in solid samples of plant origin As was determined in a number of National Institute of Standards and Technology (NIST) Standard Reference Materials (SRMs) Citrus Leaves (SRM 1572) Rice Flour (SRM 1568) Sea Lettuce [Community Bureau of Reference (BCR) Certified reference material (CRM) 2791 and Tomato Leaves (NIST SRM 1573). No sample pre-treatment except for homogeniz- ation (by shaking) and weighing was required before analysis. The moisture content of these materials was determined according to the ‘drying instructions’ given in the correspond- ing certificates and was corrected for. For the introduction of a solid sample an empty boat was first tarred using a microbalance (Sartorius M3P readability 1 pg). The amount of solid sample was subsequently directly weighed in the sample boat and the sample boat was inserted into the graphite furnace as described previously. As is described under Results and Discussion for calibration by standard addition techniques it was found necessary for liquid As spikes (5 10 or 20 p1 of As solutions of appropriate concentration) to be transferred into the sample boat and dried using an infrared (IR) lamp before solid sample loading. When using an internal standard (Sb) an aliquot of 5 or 10 pl of an Sb solution of an appropriate concentration was transferred into the sample boat using a micropipette the boat was subsequently dried using an IR lamp and was then loaded with solid sample as described In order to cover the concen- tration range from the detection limit up to a few pg g-’ of As the OmniRange device was used. By varying the ion transmission efficiency in the lens system at the exact time that a given mass to charge ratio is being measured the OmniRange device can selectively and reproducibly reduce the mass spectrometer’s sensitivity allowing measurements to be carried out at a higher concentration range.Liquid standard (As) and internal standard (Sb) solutions were prepared from commercial stock solutions with a concen- tration of 1 g 1-’ (As Fluka Buchs Switzerland; Sb Janssen Chimica Beerse Belgium). For all dilutions 0.14 moll-’ HNO obtained by dilution of concentrated HNO (purified by sub-boiling distillation) with water purified with a Milli-Q The first phase of the work consisted of optimization of the heating cycle of the furnace (ashing and vaporization tempera- system (Millipore) was used as a diluent and thoroughly cleaned volumetric flasks and pipettes were used throughout.82 Journal of Analytical Atomic Spectrometry February 1995 Vol. 10Table 1 Operating conditions and measurement parameters ICP mass spectrometer- Type R.f. power Sampling depth Carrier gas flow rate Auxiliary gas flow rate Plasma gas flow rate Lens voltages P B s 2 El Sampling cone Skimmer ETV system- Type Temperature programme Measurement parameters- Dwell time Scanning mode Sweeps per reading Readings per replicate Points per spectral peak Total measurement time Perkin-Elmer Sciex Elan 5000 1000 w 10 mm 0.710 1 min-' 1.2 1 min-' 15 1 min-' -60.6 V + 10.5 V -9.0 v + 7.4 v nickel; 1.0 mm aperture diameter nickel; 0.75 mm aperture diameter SM-30 Grun Analytische Mess-Systeme 1.'Drying' step 30 s at 120°C 2. Ashing step 35 s at 200°C 3. Intermediate step 12 s at 200°C (for switching the valve and allowing the plasma to stabilize) 4. Vaporization step 15 s at 2000°C 5. Intermediate step (no heating) (for switching the valve) 6. Cleaning step 3 s at 2600 "C 30 ms Peak hop transient 1 400 1 30 s * From load coil. RESULTS AND DISCUSSION Preliminary Studies In order to optimize the vaporization temperature the ashing temperature was kept constant at approximately 200 "C (14% of the maximum power of the furnace power supply) while increasing the vaporization temperature for every succeeding measurement.Fig. 1 shows that at a vaporization temperature of about 2000 "C (70% of the maximum power of the furnace power supply) complete vaporization of As from the sample (tomato leaves) can be assumed. Next at a constant vaporization temperature of 2000 "C the effect of the ashing temperature on the 75As+ signal intensity per mass unit sample (tomato leaves) was investigated (Fig. 2). A temperature of 200 "C provides effective ashing without causing risks of analyte losses. The signal profiles (signal intensity as a function of time) demonstrated that the 1.2 - + /+ I +/ I I 0 500 1000 1500 2000 2500 TemperaturePC Fig. 1 75As+ signal intensity per mass unit sample (tomato leaves) as a function of the vaporization temperature at a constant ashing temperature of ~ 2 0 0 ° C (14% of the maximum power of the furnace power supply).The solid line is only intended as a rough indication of the trend observed 1.2 1 1 L g 1.0 5 0.2 r. 0 c + + + 500 1000 1500 Te m pe ra t u re/" C 1 2000 Fig. 2 75As+ signal intensity per mass unit sample (tomato leaves) as a function of the ashing temperature at a constant vaporization temperature of x2000 "C (70% of the maximum power of the furnace power supply). The solid line is only intended as a rough indication of the trend observed duration of the vaporization step was sufficiently long to allow complete vaporization of As from the sample. The effect of the carrier gas flow rate was studied by monitoring the 75As+ signal intensity per mass unit solid sample (rice flour) as a function of the carrier gas flow rate.A typical signal behaviour plot as is well known from solution nebulization ICP-MS was obtained showing a maximum signal intensity at 0.710 1 min-'. For all further experiments 200 and 2000 "C were used as ashing and vaporization temperatures respect- ively and 0.710 1 min-l was selected as the carrier gas flow rate. The signal profile obtained for As in the materials analysed was observed to be of bimodal form to some extent. Both As (added as a standard for calibration purposes) and Sb (added as an internal standard to correct for fluctuations of the transport and vaporization processes and/or instrument insta- bility) spikes were observed only to show an analogous profile on condition that these liquid spikes (aliquots of As or Sb Journal of Analytical Atomic Spectrometry February 1995 Vol.10 83solutions of known concentration) were previously dried (using an IR lamp) before the solid sample was introduced into the sample boat. Fig. 3(u) shows the 7 5 A ~ + and "'Sb' signal profiles for a liquid sample (solution) containing As and Sb. Clearly for both analytes only one maximum is observed. Fig. 3(b) shows the signal profiles for 7 5 A ~ + and 121Sb+ in a case where the Sb spike has been dried prior to the introduction of a solid sample of rice flour (no As spike added). Under these conditions the 7 5 A ~ f (coming exclusively from the solid sample) and the l2lSb+ (coming exclusively from the Sb spike) profile are now observed to be of (analogous) bimodal form.On the other hand an Sb spike added only after solid sample loading gives a profile analogous to that observed for a liquid sample as presented in Fig. 3(a) and thus strongly deviating from that for As coming from the solid sample. An As spike dried before solid sample loading contributes to both peaks originating from As coming from the solid sample without significantly affecting the ratio of their relative sizes [Fig. 3 (c)] . As a result it can be assumed that the As spike if dried previously gives rise to an analogous 7 5 A ~ + profile as observed for the solid sample. On the other hand when liquid As spikes were only added after solid sample loading the shape of the bimodal 75As+ profile was observed to be altered indicating a different contribution of As coming from the spike to the two peaks of the As profile for the solid sample.Hence under these conditions a different behaviour between As coming from the solid sample and from the liquid spike can assumed The latter conditions are clearly less suited accurate quantification hence for further measurements invc ing the addition of Sb and/or As solutions spikes were a h dried previously to sample loading. Although the exact sh of the 75As+ profile was observed to be different for all SR investigated similar conclusions could be drawn for e material under consideration on condition that As and spikes were dried prior to solid sample loading the sii profiles for both Sb and As spikes were observed to analogous to (and hence dependent on) that observed for coming from the solid sample.The reason for this behavj is not clear and a detailed explanation would require n investigation. On plotting the 75A~+ signal intensity as a function of sample mass no linear graph is obtained as is illustrated sea lettuce in Fig. 4(u). Since however for Sb added as internal standard the signal intensity is suppressed to the Si extent as for As when increasing the sample mass plotting signal ratio (75A~+/121Sb+) as a function of the sample n results in a linear graph [Fig. 4(b)]. For larger sample ma (in the case of sea lettuce >1.4mg) the curvature see1 Fig.4(a) was even more pronounced such that the CI became almost horizontal. For these larger sample masses could no longer accurately correct for these effects.As a re the sample sizes were always chosen relatively small (< 1.2 (a) 150 100 50 10 15 0 5 10 15 5 10 Time/s 15 Fig. 3 75As+ and lzlSb+ signal intensities as a function of time (signal profiles) for (a) a liquid sample solution containing As and Sb; (b) a sample of rice flour inserted in a sample boat containing a previously dried (IR lamp) Sb spike (no As spike added). (c) 7 5 A ~ + signal inten as a function of time (signal profiles) for a solid sample of rice flour (no As spike added) and a solid sample of rice flour inserted in a sa boat containing a previously dried (IR lamp) As spike 84 Journal of Analytical Atomic Spectrometry February 1993 Vol. 10+ v) 2 r + 3 h 3.0 2.5 2.0 1.5 1 .o 0.5 0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 Sample mass/mg Fig.4 (a) 75As+ signal intensity and (b) 75As+ "lSb+ signal ratio as a function of the sample mass of Sea Lettuce (BCR CRM 279) and if no internal standard was used as close to one another as practically possible. Possibly the behaviour established is to be ascribed to matrix effects in the plasma and/or during the ion beam formation process caused by matrix components which are not removed during ashing and are vaporized and transported into the central channel of the ICP together with As. Finally since on the addition of increasing amounts of As standard solution to the solid samples linear calibration graphs were obtained the potential of the technique was investigated by establishing the figures of merit. Figures of Merit On condition that sample sizes were chosen to be relatively small (< 1.2 mg) and as close as possible to one another (in mass) both for the 75As+ signal intensities per unit mass of sample and for the signal ratios (75A~+/121Sb+) per unit mass of sample a relative standard deviation (S,) of <15% (five measurements) could be obtained in all instances.It is believed that the inhomogeneity of the material analysed (small sample sizes!) limits the precision attainable since for some materials (e.g for sea lettuce) significantly better S values are obtained than for other whereas the S for liquid samples was seen to be typically about 5% (five measurements). As a result for all determinations at least five subsamples were analysed. Although rather to be considered as a disadvantage in general the small sample sizes in solid sampling ETV-ICP-MS can be advantageous for homogeneity studies.Limits of detection for As were calculated applying the 3s criterion using 'empty boats' as blanks (ten measurements) and standard reference materials with certified As contents as external standard. Even after repetitive heating of a sample boat to temperatures > 2000 "C the blank value was observed readily to amount to a total of a few thousand integrated ion counts with S ~ 5 % . The sensitivity (the total number of integrated ion counts per unit mass of As) was observed to be dependent on (i) the sample mass [see Fig. 4(a)] and ( i i ) the solid material under consideration. For a typical sample mass of 0.5-1 mg sensitivities ranging from 5 x lo5 to lo6 ng-' As are typical.These values lead to an absolute limit of detection for As of about 1 pg corresponding to a relative limit of detection of about 1 ng g-' for a typical sample mass of 1 mg. However it should be stressed that new pyrolytic graphite- coated graphite tubes and sample boats should be submitted to repeated cleaning by heating to temperatures > 2000 "C since the initial blank value especially for Sb was observed to exceed enormously the blank value finally obtainable. Finally before starting the As determination in the SRMs the potential interference of 40Ar35C1+ on 75A~+ was investi- gated by monitoring both 7 5 A ~ + and 40Ar37C1+. These experi- ments showed that even on addition of large amounts of C1 (up to 50 pg and exceeding the C1 content of the samples) no interference on 7 5 A ~ + could be established.Determination of As in SRMs of Plant Origin For the determination of As in Citrus Leaves (NBS SRM 1572) Rice Flour (NBS SRM 1568) Sea Lettuce (BCR CRM 279) and Tomato Leaves (NBS SRM 1573) several methods of calibration were tested including external calibration using liquid and solid standards and single standard addition. The performance of these calibration techniques was evaluated by comparing the results obtained with one another and with the corresponding certified values. All results obtained for the As content in the SRMs analysed are summarized in Table 2. Each figure presented is the result of at least two independent determinations for each of which at least five subsamples were measured.Further details concerning the measuring sequences will be discussed for each individual method of calibration. For each result presented a standard deviation is also given calculated as the mean of the standard deviations obtained for the replicate determinations. Table2 ETV-ICP-MS results for the determination of As in standard reference materials of plant origin by various calibration methods. All results presented are expressed in p g g-' Certified value f 95 % confidence limit Mean (standard deviation) external calibration using liquid standard solutions Mean (standard deviation) external calibration using SRMs with certified As content Mean (standard deviation) single standard addition based on results for (75As + /121Sb + ) addition based on results for 75Asf Mean (standard deviation) Single standard Citrus leaves Rice flour Sea lettuce (NBS SRM 1572) (NBS SRM 1568) (BCR CRM 279) 3.1 k0.3 2.8 (0.4) 0.41 & 0.05 3.09 k0.20 0.46 (0.05) 3.1 (0.5) 3.0 (0.5) - - using BCR CRM 279 3.3 (0.4) 0.34 (0.05) 3.2 (0.4) 3.2 (0.9) 0.36 (0.06) 3.1 (0.3) Tomato leaves (NBS SRM 1573) 0.27 & 0.05 0.35 (0.05) 0.27 (0.04) using NBS SRM 1568 0.29 (0.04) 0.26 (0.04) Journal of Analytical Atomic Spectrometry February 1995 Vol.10 85External calibration using liquid standard solutions If completely reliable external calibration using a liquid stan- dard solution would be the most straightforward and fastest way to determine the As content in the materials analysed. A measurement sequence can in this instance be limited to three measurements of the blank value five measurements of the solid sample to be analysed and five measurements of the liquid standard solution.Of course based on the results for the 75A~+ signal intensity as a function of the sample mass [Fig. 4(a)] it is essential to use an internal standard to correct for matrix effects observed with increasing sample mass so that Sb was added as an internal standard to the blanks samples and standards. Although it was observed that liquid standard solutions give rise to a signal profile of a significantly different form than the signal profiles observed when vaporizing solid material [compare Fig. 3(a) with Fig. 3(b)] the results obtained for the As content in the SRMs analysed are in fair agreement with the certified values (Table 2).This reasonable agreement indicates that the internal standard Sb succeeds in correcting fairly accurately for these vastly differing vaporizing conditions and for possible differences in transport efficiency and/or plasma processes (matrix effects) illustrating the power of the concept of internal standardization. External calibration using SRMs with certified As content The use as a calibrant of an SRM with a similar matrix composition and analyte content to that of the samples to be analysed is a well known procedure in solid sampling. Excellent results for the As content of Tomato Leaves (NBS SRM 1573) using Rice Flour (NBS SRM 1568) as a standard and for Citrus Leaves (NBS SRM 1572) using Sea Lettuce (BCR CRM 279) as a standard were only obtained on condition that Sb was used as an internal standard.Results obtained without internal standardization could differ as much as by a factor of two so that the use of an internal standard was clearly imperative. As a result Sb was added as an internal standard both to the blank (three measurements) and to the two SRMs involved (five measurements). Results obtained using SRMs as a calibrant appear to be in slightly better agreement with the certified values than those obtained using external calibration with a liquid standard. This can probably be attributed to the obvious fact that the vaporizing transport and plasma con- ditions differ less for two solid samples of fairly similar composition than for a solid sample and a liquid sample. For the calculation of the standard deviation when using a standard reference material with certified As content as an external calibrant the uncertainty on the certified value was not taken into account leading to underestimated values for the standard deviations (Table 2).Although the excellent results obtained clearly illustrate its potential this approach has several drawbacks. An important consequence of this calibration method is that solid sampling ETV-ICP-MS would not be an independent method as one has to rely on certified values based on results obtained by other analytical tech- niques. Moreover the uncertainty on the certified analyte content is in general much larger than the uncertainty on the concentration of a liquid standard solution. Further some information on the sample matrix is always required and finally a suitable reference material (similar to the sample in matrix composition and analyte content) is probably not available for all problems that could be encountered.Single standard additions For solid samples single standard addition is very similar to external calibration with a liquid standard with the important difference that the standard is 'matrix matched'. As a result calibration using the method of single standard addition is also a very fast method requiring only three measurements of the blank five measurements of the sample and five measure- ments of the sample to which an analyte spike of appropriate concentration is added. The results obtained are in very good agreement with the certified values when using an internal standard (Table 2).On condition that the sample masses were chosen to be as close to one another as practically possible accurate results could also be obtained using single standard addition without the use of an internal standard. Although not imperative in this instance the use of an internal standard is considered advantageous as it allows a more accurate correction for the blank (cf. matrix effects) which is of major importance if the blank value contributes significantly to the total signal and allows one to correct for signal drift and/or instrument instability for fluctuations in the vaporization and transport processes and for possible differences in the magni- tude of matrix effects caused by variation of the sample mass in a series of measurements.Finally the merits of multiple standard addition and the simplified generalized standard addition method (GSAM)44745 were briefly examined. Both methods are very similar to the method of single standard addition but give rise to longer measurement sequences and require the addition of larger amounts of As spike which is not desirable. During these relatively long measuring sequences the As blank value was seen to increase steadily (memory effects) so that short measur- ing sequences not longer than ten successive measurements (other than blank determinations) are to be preferred. Blank values could only be reduced to the initial values after repetitive cleaning by heating to temperatures > 2000 "C. Although not tested for all materials the results obtained using multiple standard addition or the GSAM method were observed not to be superior to those obtained using single standard addition.Table 2 ETV-ICP-MS results for the determination of As in standard reference materials of plant origin by various calibration methods. All results presented are expressed in pg g-' Certified value & 95% confidence limit Mean (standard deviation) external calibration using liquid standard solutions Mean (standard deviation) external calibration using SRMs with certified As content Mean (standard deviation) single standard addition based on results for (75A~+ /l2'Sb+) addition based on results for 75As+ Mean (standard deviation) Single standard Citrus leaves Rice flour Sea lettuce (NBS SRM 1572) (NBS SRM 1568) (BCR CRM 279) 3.1 f 0.3 2.8 (0.4) 0.41 & 0.05 0.46 (0.05) 3.1 (0.5) 3.09 f 0.20 3.0 (0.5) - - using BCR CRM 279 3.3 (0.4) 0.34 (0.05) 3.2 (0.4) 3.2 (0.9) 0.36 (0.06) 3.1 (0.3) Tomato leaves (NBS SRM 1573) 0.27 k 0.05 0.35 (0.05) 0.27 (0.04) using NBS SRM 1568 0.29 (0.04) 0.26 (0.04) 86 Journal of Analytical Atomic Spectrometry February 1995 Vol.10CONCLUSIONS ETV-ICP-MS has been successfully applied to the determi- nation of trace amounts of As in solid materials of plant origin. Although several calibration methods offered possibilities for accurate quantification (mean deviation between ETV-ICP-MS results and certified values < lo%) single standard addition was assessed to be the most reliable and practicable method. The use of an internal standard was studied and was observed to range from advantageous (standard addition methods) to imperative (external calibration methods) depending on the calibration method used.During relatively long analysis sequences the blank signal was seen to increase slowly but steadily (memory effects) so that blank values had to be carefully corrected for or restored to the initial values by repetitive heating of the furnace. This is at present a limitation for straightforward routine use. Future efforts in our laboratory will be mainly focused on the determination of other elements and a more pronounced exploitation of the multi-element capabilities of ICP-MS. 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ISSN:0267-9477    

DOI:10.1039/JA9951000081

出版商:RSC    

年代:1995

数据来源: RSC